201229330 六、發明說明： 本發明係在由美國能源部（DOE)所給予之能源部合約 第DE-AC36-98GO100336號之國家可更新能源實驗室 (NREL)副合約第ZDO-2-30628號的政府支援下完成者。美 5 國政府對本發明具有某些權利。 相關申請案 本發明主張2006年1月20日申請之美國暫時申請案第 60/760,453號、2006年5月30曰申請之美國暫時申請案第 60/808,954號、2006年8月24日申請之美國暫時申請案第 10 60/839,672號、及2006年8月24日申請之美國暫時申請案第 60/839,670號之優先權，且其全部内容在此加入作為參考。 L發明所屬之技術領域3 技術領域 本發明大致係有關於光電領域且有關於用以製備用於 15 光電應用之鑄態矽的方法及裝置。本發明更有關於可用於 製備如光電電池與其他半導體元件等元件之新形態鑄態 矽，且該新矽可具有單晶結構且可利用一鑄造法製備。 C先前技3 背景資訊 20 光電電池將光轉換成電流，且光電電池之其中一最重 要數值是它將光能轉換成電能之效率。雖然光電電池可以 由各種半導體材料製成，但是通常使用的是矽，這是因為 它很容易以合理之價格取得，且因為它對於用於製備光電 電池具有電、物理與化學性質之適當平衡性。 201229330 之用s吾卓晶石夕”表示具有 在用以製備光電電池之習知程序中，石夕進料與一用 以誘發正或貞導·叙㈣（或摻_)混合、熔化且接著 依據個财晶粒之晶粒尺寸，藉由將結㈣拉出-炫化區 域成為早晶歡鑄塊(透過柴式“A她ki)(cz)或浮動區 (FZ)法)或鑄成多結晶矽或多晶矽之塊或“碑”。在此所使用 致晶體方位之單一結晶石夕 個 15 20 體’此外’習知多晶⑪表示具有⑽級晶粒尺寸分布且具有 多數位在-石夕體内之任意方位晶體的結晶石夕。但是，在此 所使用之用語“依幾何形狀規則排列之多晶石夕”(以下稱為 “幾何型多晶們表示本發明實施例之結㈣，該結晶石夕具 有依幾何形狀規則排列之cm級晶粒分布，且多數規則排列 晶體位在-石夕體内。例如，在幾何型多晶石夕中各晶粒通 予具有一大約0,25cm2至2,500cm2之平均橫截面積及可以與 该矽體一樣大之高度。例如，該高度可以與該矽體垂直於 *亥橫截面之平面的尺寸一樣大，並且在幾何型多晶矽體内 之晶粒方位係依據預定方位加以控制。此外，在此所使用 之用語“多晶矽”表示具有微米級晶粒尺寸之結晶矽及多數 位在一矽體内之晶粒方位。例如，該等晶粒通常具有大約 次微米至次毫米之平均值尺寸（如，個別晶粒可能無法用肉 眼看到），且晶粒方位在其中任意地分布。在前述程序中， 該等鑄塊或塊利用習知之切割或鋸切方法切成亦稱為晶圓 之薄基材。接著’可將這些晶圓加工成光電電池。此外， 在此所使用之用語“近似單晶矽，，表示結晶矽體，且該結晶 矽體在大於該50%之矽體體積中具有一致晶體方位，例 4 201229330 如，這近似單晶矽可包含與一多晶區域相鄰之單晶矽體， 或它可包含一部份或完全含有其他晶體方位之較小矽晶體 的大立速續一致矽結晶，其中該較小晶體不會佔全部體積 之50%以上。該近似單晶矽宜包含不會佔全部體積之25%以 5上之較小晶體。較佳地，該近似單晶矽可包含不會佔全部 體積之10%以上之較小晶體。更佳地，該近似單晶矽可包 含不會佔全部體積之5%以上之較小晶體。 用於製備光電電池之單晶矽通常是利用CZ或FZ法製 造’而這兩種方法係會產生一石夕晶之圓柱形晶述之製程。 10對cz製程而言，該晶坯被緩緩地拉出一炫融石夕池’且對FZ 製程而言’固態物質經由一炼化區送入且在該熔化區之另 15 一側再固化。以這些方式製造之單晶矽晶坯含有徑向分布 之雜質與缺陷’例如，氧誘發堆疊缺陷（OSF)之環及格隙或 空位團之“旋滿”缺陷。即使有這些雜質與缺陷，單晶矽仍 疋一般用以製造光電電池之較佳矽源，因為它可以用來製 造尚效率之太陽能電池。但是，單晶矽之製造成本比使用 如前述之習知方法的習知多晶石夕高。 用以製備光電電池之習知多晶矽通常是利用一鑄造法 盤、皮 & ’且用於製備一習知多晶矽之鑄造製程在光電技術中 疋習知的。伟士 一 ^ 4 5之，在這些製程中，將溶融碎裝在一如石 二坩堝之坩堝中，且在受控制之情形下加以冷卻，使在其 中之石夕結曰 ，a 。曰曰。所得到之多晶矽塊通常會被切成多數磚，而 具有與欲用以製備一光電電池之晶圓尺寸相同或接 近之橫截& 、 ’且該等磚會被鋸切或以其他方式切割成前述 20 201229330 晶圓。依此方式製成之多晶矽是一晶粒之聚結體，其中， 在由其製成之晶圓内，該等晶粒彼此之間的方位有效地任 意分布。 在習知多晶矽或多結晶矽中之晶粒任意分布方位使所 5 得之晶圓表面難以紋理化，而紋理化可利用減少光反射與 增加通過一電池表面之光能吸收來改善光電電池之效率。 此外’在習知多晶矽晶粒間之邊界中的“扭折”會使結構缺 陷集結成錯位之團或線。這些錯位與它們會吸引之雜質將 會使在由習知多晶矽製成之作用中光電電池中的電荷載子 10 再結合，且這會使電池之效率降低。即使考慮在由習知方 法製成之單晶矽中存在之徑向缺陷分布，與由單晶石夕製成 之等效光電電池相較，由這種多晶碎製成之光電電池仍具 有較低之效率。但是，因為製造習知多晶矽較簡單且成本 較低，並且在電池製程中可有效鈍化缺陷’多晶矽是用於 15製備光電電池之較廣泛使用的矽型態。 某些以往的鑄造方法會使用一“冷壁，，坩堝來進行晶體 成長’且用s吾“冷壁，，表示在該掛禍壁上或在該掛堝壁中之 感應線圈業經水冷，且可以開設溝槽，因此通常保持在 100°C以下。該坩堝壁可以緊臨在該等線圈與進料之間，且 2〇該坩堝壁並未熱絕緣，且因此可保持與該等已冷卻線圈熱 平衡。故矽並非由來自該坩堝壁之輻射熱加熱，因為在該 #禍中之⑦的感應加熱表示⑦係由因感應而在其中流動之 電流直接加熱。依此方式，該掛竭壁仍處於該石夕之炼化溫 度以下，且被視為是相對於該溶融石夕是“冷的，，。在感應地 6 201229330 加熱之熔融矽固化時，這些坩堝之冷壁作為散熱器，且由 於對該等冷壁之輻射，該等讀塊迅速地冷卻。因此，一初 始固化前面會迅速地弯曲，立晶體成核在該铸塊侧邊發生 且朝該鑄塊中心對角地成長，並且使保持垂直與依幾何形 5狀規則排列之晶種成長過程中斷或無法保持實質平坦固化 前面。 由前所述可知，需要有一種可用以製備光電電池之改 良矽形態，且亦需要一種可以在一比以往用於製造單晶矽 之方法更快且更便宜之方法中製備的矽。本發明提供這種 10 矽與這些方法。201229330 VI. INSTRUCTIONS: This invention is in the National Renewable Energy Laboratory (NREL) Subcontract No. ZDO-2-30628 of the Department of Energy Contract No. DE-AC36-98GO100336 awarded by the US Department of Energy (DOE). Completed by government support. The governments of the United States have certain rights in the invention. RELATED APPLICATIONS The present application claims the application of the U.S. Provisional Application No. 60/760,453, filed on Jan. 20, 2006, and the application of the U.S. Provisional Application No. 60/808,954, filed on August 24, 2006 Priority is claimed in U.S TECHNICAL FIELD OF THE INVENTION The present invention relates generally to the field of optoelectronics and to methods and apparatus for preparing as-cast crucibles for use in 15 optoelectronic applications. More particularly, the present invention relates to a new form of as-cast crucible that can be used to fabricate components such as photovoltaic cells and other semiconductor components, and which can have a single crystal structure and can be prepared by a casting process. C Prior Art 3 Background Information 20 Photovoltaic cells convert light into electrical current, and one of the most important values of photovoltaic cells is the efficiency of converting light energy into electrical energy. Although photovoltaic cells can be made from a variety of semiconductor materials, germanium is commonly used because it is readily available at reasonable cost and because it has the right balance of electrical, physical, and chemical properties for the fabrication of photovoltaic cells. . 201229330 “Ussu 晶晶晶夕” means that in the conventional procedure for preparing photovoltaic cells, the Shixi feed is used to induce the mixing or melting of the positive or negative conductive (four) (or mixed) and then According to the grain size of the grain of the grain, by pulling out the junction (four) - the illusion zone becomes an early crystal casting block (through the Chai "A her ki" (cz) or floating zone (FZ) method) or cast A block or "stamp" of polycrystalline ruthenium or polycrystalline ruthenium. Here, a single crystallized crystal orientation of the crystal orientation is used. Further, the conventional polycrystal 11 represents a crystallite having a (10)-order grain size distribution and having a crystal orientation of any orientation in the body of the stone body. However, the term "polycrystalline stone arranged regularly according to geometrical shape" (hereinafter referred to as "geometric polycrystalline" means the knot (4) of the embodiment of the present invention, which has a geometrical regular arrangement. Cm-level grain distribution, and most of the regular arrangement of crystals in the body of the stone. For example, in the geometric polycrystalline stone, each grain pass has an average cross-sectional area of about 0,25cm2 to 2,500cm2 and can The height is as large as the body. For example, the height may be as large as the size of the plane perpendicular to the plane of the cross section, and the grain orientation in the geometric polysilicon is controlled according to a predetermined orientation. As used herein, the term "polycrystalline germanium" means a crystalline germanium having a micron-sized grain size and a grain orientation of a majority in a crucible. For example, the grains generally have an average value of from about submicron to sub-millimeter. Dimensions (eg, individual grains may not be visible to the naked eye), and the grain orientation is arbitrarily distributed therein. In the foregoing procedure, the ingots or blocks are cut by conventional cutting or sawing methods. A thin substrate for the wafer. Then these wafers can be processed into photovoltaic cells. In addition, the term "approximately single crystal germanium" is used herein to mean a crystalline germanium, and the crystalline germanium is greater than the 50%. Uniform crystal orientation in body volume, Example 4 201229330 For example, this approximately single crystal germanium may comprise a single crystal body adjacent to a polycrystalline region, or it may contain a portion or a portion of other crystal orientations. The large vertical velocity of the crystal is consistent with crystallization, wherein the smaller crystal does not account for more than 50% of the total volume. The approximate single crystal yttrium contains less than 25% of the total volume to a smaller crystal of 5. The approximate single crystal germanium may comprise a smaller crystal which does not account for more than 10% of the total volume. More preferably, the approximate single crystal germanium may comprise a smaller crystal which does not account for more than 5% of the total volume. The single crystal germanium for the preparation of photovoltaic cells is usually produced by the CZ or FZ method, and the two methods produce a cylindrical crystallographic process. In the case of the cz process, the crystal blank is slowly pulled. Out of a dazzling melting stone eve pool' and for the FZ process 'solid The material is fed through a refinery zone and resolidified on the other 15 side of the melt zone. The single crystal twins produced in these manners contain radially distributed impurities and defects 'for example, oxygen induced stack defects (OSF) The "spinning" defect of the ring and the gap or vacancy. Even with these impurities and defects, the single crystal germanium is still the preferred source for the manufacture of photovoltaic cells because it can be used to make solar cells that are still efficient. The manufacturing cost of the single crystal germanium is higher than that of the conventional polycrystalline silicon using the conventional methods as described above. Conventional polycrystalline germanium used to prepare photovoltaic cells is usually made using a casting disk, leather & The casting process of polycrystalline germanium is well known in optoelectronic technology. In these processes, the melt is crushed into a crucible and cooled under controlled conditions. To make the stone stagnation in it, a. Hey. The resulting polycrystalline germanium block will typically be cut into a plurality of bricks having the same or close cross-section & the size of the wafer to be used to prepare a photovoltaic cell, and the bricks will be sawed or otherwise cut. Into the aforementioned 20 201229330 wafers. The polycrystalline silicon produced in this manner is a grained agglomerate in which the orientations of the crystal grains are effectively distributed to each other in a wafer made therefrom. The arbitrary orientation of the crystal grains in the conventional polycrystalline germanium or polycrystalline germanium makes the surface of the obtained wafer difficult to be textured, and the texturing can improve the photovoltaic cell by reducing light reflection and increasing absorption of light energy through a battery surface. effectiveness. Furthermore, "kneading" in the boundaries between conventional polycrystalline germanium grains can cause structural defects to build up into misaligned clusters or lines. These misalignments and the impurities they attract will recombine the charge carriers 10 in the photovoltaic cell during the action made by conventional polysilicon, and this will reduce the efficiency of the cell. Even considering the radial defect distribution present in a single crystal germanium made by a conventional method, a photovoltaic cell made of such a polycrystalline chip has a photocell compared to an equivalent photovoltaic cell made of monocrystalline Lower efficiency. However, since the fabrication of conventional polysilicon is relatively simple and cost-effective, and can effectively passivate defects in the battery process, polycrystalline germanium is a more widely used germanium type for the preparation of photovoltaic cells. Some conventional casting methods use a "cold wall, 坩埚 to carry out crystal growth" and use "winter wall" to indicate that the induction coil on the wall or in the wall of the wall is water-cooled, and Grooves can be created and are therefore typically kept below 100 °C. The crucible wall can be immediately adjacent the coils and the feed, and the crucible wall is not thermally insulated and thus can remain thermally balanced with the cooled coils. Therefore, the crucible is not heated by the radiant heat from the crucible wall, because the induction heating in the ? 7 indicates that the 7 series is directly heated by the current flowing therein due to induction. In this way, the wall is still below the refining temperature of the stone, and is considered to be "cold" relative to the molten stone, when the inductively heated layer of 2012 201230 is solidified, these The cold wall of the crucible acts as a heat sink, and due to the radiation of the cold walls, the reading blocks are rapidly cooled. Therefore, an initial solidification front is rapidly bent, and a vertical crystal nucleation occurs on the side of the ingot and The center of the ingot grows diagonally, and the growth process of the seed crystals that are kept perpendicular and regularly arranged in a geometric shape is interrupted or cannot be maintained substantially flat and solidified. As described above, there is a need for an improvement in the preparation of photovoltaic cells. The crucible morphology also requires a crucible that can be prepared in a faster and cheaper process than previously used to make single crystal crucibles. The present invention provides such a crucible and these methods.
【明内^§1 J 發明概要 所實施與廣義地說明之本發明提供一種用以製備鑄態 矽之方法，包含：將熔融矽放置在一容器中以接觸至少一 U石夕種晶’而該容器具有一或多個力口熱到至少該石夕之炫化溫 度之側壁及至少一用以冷卻之壁；及藉由將該溶融石夕冷卻 以控制結晶而形成固態之單晶矽體，且該單晶矽體可選擇 性地具有至少兩各至少為大約1〇(；〇1之尺寸，其中該形成步 驟包括至少在開始時平行前述至少一用以冷卻之壁之熔融 2〇矽邊緣處形成一固液界面，且在冷卻時，該界面受到控制 而朝一可增加該熔融矽與該至少—用以冷卻之壁間之距離 的方向移動。在此應了解的是該坩堝之其中一壁可以是該 坩堝之底部。 本發明之一實施例亦提供—種用以製備鑄態矽之方 201229330 法，包含：將多數單晶矽種晶之幾何型結構放置在一坩堝 之至少一表面上，且該掛禍具有一或多個加熱到至少該石夕 之熔化溫度的側壁及至少一用以冷卻之壁，其中該幾何型 結構包括緊密堆疊之多邊形；放置熔融矽，使其接觸該單 5 晶矽種晶之幾何型結構；及藉由將該熔融矽冷卻以控制結 晶而形成固態之單晶矽體，且該單晶矽體可選擇性地具有 至少兩各至少為大約10cm之尺寸，其中該形成步驟包括至 少在開始時平行前述至少一用以冷卻之壁之熔融矽邊緣處 形成一固液界面，且在冷卻時，該界面受到控制而朝一可 10 增加該熔融矽與該至少一用以冷卻之壁間之距離的方向移 動。 本發明之另一實施例亦提供一種用以製備鑄態矽之方 法，包含：以一預定圖案將多數單晶矽種晶排列在一坩堝 之至少兩表面上；放置該熔融矽，使其接觸該等單晶矽種 15 晶；及藉由自前述該坩堝之至少兩表面將該熔融矽冷卻以 控制結晶而形成固態之單晶矽體，且該單晶矽體可選擇性 地具有至少兩各至少為大約10cm之尺寸，其中該形成步驟 包括在冷卻時控制一位於熔融矽邊緣處固液界面，使之朝 一可增加該熔融矽與該坩堝之至少兩表面間之距離的方向 20 移動。 本發明之再一實施例亦提供一種用以製備鑄態矽之方 法，包含：放置矽進料，使其接觸在至少一表面上之至少 一單晶矽種晶；加熱該矽進料與該至少一單晶矽種晶至矽 之熔化溫度；控制該加熱，使前述至少一單晶矽種晶不會 8 201229330 70王熔化且"亥控制包含維持一當在該坩煱中另一處到達 雜U後，在!㈣粉卜表面上測量時1ΔΤ大約等於或 J於0.1 C/min，及—旦前述至少一單晶矽種晶部分地熔 化’藉由冷卻該矽而形成固態之單晶矽體。 本發月之又一實施例亦提供-種用以製備鑄態石夕之方 法L3將夕數單晶矽種晶之幾何型結構放置在一坩堝 之至V纟面上’其中該幾何型結構包括緊密堆疊之多邊 形，放置6亥石夕進料，使其接觸在該至少-表面上之前述多 數單晶石夕種晶；加熱該石夕進料與前述多數單晶石夕種晶至石夕 10之溶化溫度；控制該加熱，使前述多數單晶石夕種晶不會完 王熔化’且5玄控制包含維持一當在該闕中另一處到達該 炫化溫度後，在該職絲面均量時之ΛΤΑ約等於或小 於O.PC/min ;及-旦前述至少—單晶㈣晶部分地炼化， 藉由冷卻該矽而形成固態之單晶矽體。 15 I發明之另—實施例亦提供-種用以製備鳞態石夕之方 法’包含.以-預定圖案將多數單晶石夕種晶排列在一掛禍 之至少兩表面上；放置石夕進料，使其接觸在前述至少兩表 面上之多數單晶石夕種晶；加熱該石夕進料與前述多數翠晶石夕 種晶至石夕之熔化溫度；控制該加熱，使前述多數單晶石夕種 2〇晶不會完全熔化，且該控制包含維持一當在該輯中另一 處到達該熔化溫度後’在該_外表面±測量時之Μ大約 等於或小於G.TOmin ;及-旦前述至少—單晶㈣晶部分 地熔化，藉由冷卻該矽而形成固態之單晶矽體。 本發明之再-實施例亦提供一種用以製備禱態石夕之方 201229330 法，包含：放置熔融矽在一容器中，使其接觸至少一矽種 晶，而該容器具有一或多個加熱到至少該矽之熔化溫度之 側壁，且該至少一矽種晶配置成可覆蓋該容器表面之整個 或實質上整個面積；及藉由將該熔融矽冷卻以控制結晶而 5 形成固態之單晶矽體，且該單晶矽體可選擇性地具有至少 兩各至少為大約1 〇cm之尺寸。 本發明之又一實施例亦提供一種連續單晶矽體，且該 單晶矽體沒有或實質上沒有徑向分布之雜質與缺陷，並且 具有至少兩各為至少大約25cm之尺寸及一至少大約20cm 10 之第三尺寸。 本發明之另一實施例亦提供一種連續單晶矽體，且該 單晶石夕體具有大約2xl016atoms/cm3至5xl017atoms/cm3之碳 濃度、不超過5xl017atoms/cm3之氧浪度、至少 lxl015atoms/cm3之氮濃度，並且具有至少兩各為至少大約 15 25cm之尺寸及一至少大約20cm之第三尺寸。 本發明之又一實施例亦提供一種連續鑄態單晶矽體， 且該單晶矽體具有至少兩各為至少大約35cm之尺寸。 本發明之再一實施例亦提供一種太陽能電池，包含： 一晶圓，係由一連續單晶矽體形成，且該單晶矽體沒有或 20 實質上沒有徑向分布之雜質與缺陷，並且該單晶矽體具有 至少兩各為至少大約25cm之尺寸及一至少大約20cm之第 三尺寸；一p-n接面，係在該晶圓中者；一可選擇性設置之 抗反射塗層，係在該晶圓之表面上；至少一層，係選擇性 選自於一背面場（back surface field)與一純化層者；及導電 10 201229330 接頭，係位在該晶圓上者。 本發明之另一實施例亦提供一種太陽能電池，包含： 一晶圓，係由一連續鑄態單晶矽體形成，且該單晶矽體具 有至少兩各為至少大約35咖之尺寸；_ρ_η接面，係在該晶 圓中者；-可選擇性設置之抗反射塗層，係在該晶圓之表 面上；至少一層，係選擇性選自於一背面場與一鈍化層者； 及導電接頭’係位在該晶圓上者。 本發明之又一實施例亦提供一種太陽能電池，包含： 一連續單晶矽晶圓，係由一連續鑄態單晶矽體形成，且該 10晶圓具有至少一至少大約為50_之尺寸，並且該單晶矽體 具有至少兩各為至少大約25cm之尺寸及一至少大約2〇cm 之第二尺寸；一 p_n接面，係在該晶圓中者；一可選擇性設 置之抗反射塗層，係在該晶圓之表面上；至少一層，係選 擇性選自於一背面場與一鈍化層者；及導電接頭，係位在 15 該晶圓上者。 本發明之另一實施例亦提供一種晶圓’包含係由一連 續單晶矽體形成之矽，且該單晶矽體沒有或實質上沒有徑 向分布之雜質與缺陷，並且該單晶矽體具有至少兩各為至 少大約25cm之尺寸及一至少大約2〇cm之第三尺寸。 本發明之再一實施例亦提供一種晶圓，包含由一連續 單晶矽體形成之矽，且該晶圓具有至少一至少大約為5〇咖 之尺寸，並且該單晶矽體具有至少兩各為至少大約25〇〇1之 尺寸及一至少大約2〇cm之第三尺寸。 本發明之又一貫施例亦提供一種用以製備鑄態石夕之方 201229330 =’包含：放錄融⑦於—容器中’使其接觸至少一石夕種 日日而遺各器具有一或多個加熱到至少該矽之溶化溫度之 u壁及至少-用以冷卻之壁；及藉由將該溶㈣冷卻以控 制結晶而形成固態之近似單晶矽體，且該近似單晶矽體可 5選擇性地具有至少兩各至少為大約1〇cm之尺寸，其中該形 成步驟包括至少在開始時平行前述至少一用以冷卻之壁之 炫融石夕邊緣處形成一固液界面，且在冷卻時，該界面受到 控制而朝—可增加該熔融矽與該至少一用以冷卻之壁間之 距離的方向移動。 1〇 本發明之另一實施例亦提供一種用以製備鑄態矽之方 法，包含：放置熔融矽於一容器中，使其接觸至少一矽種 日 曰曰而°玄各器具有一或多個加熱到至少該石夕之炫化溫度之 側壁，且該至少一矽種晶配置成可覆蓋該容器表面之整個 或實質上整個面積；及藉由將該熔融矽冷卻以控制結晶而 5形成固態之近似單晶矽體，且該單晶矽體可選擇性地具有 至少兩各至少為大約10cm之尺寸。 本發明之又一實施例亦提供一種連續近似單晶石夕體， 且該近似單晶矽體沒有或實質上沒有徑向分布之雜質與缺 I5» ’並且具有至少兩各為至少大約25cm之尺寸及一至少大 20約20cm之第三尺寸。 本释明之另一實施例亦提供一種連續近似單晶石夕體， 且该近似早晶妙體具有大約2x10l6atoms/cm3至 5xl017atoms/cm3之碳濃度、不超過5xl017atoms/cm3之氧濃 度、至少lxlOl5atoms/cm3之氮濃度，並且具有至少兩各為 12 201229330 至少大約25cm之尺寸及一至少大約2〇咖之第三尺寸。 本發明之又-實施例亦提供一種連續近似單晶石夕體， 且該近似單晶石夕體具有至少兩各為至少大約设狀尺寸。 本發明之再—實施例亦提供一種太陽能電池，包含： 5 一晶圓，係由—連續近似單晶矽體形成，且該近似單晶矽 體沒有或實質上沒有徑向分布之雜質與缺陷，並且該單晶 石夕體具有至少兩各為至少大約25cm之尺寸及一至少大約 20cm之第三尺寸；一ρ·η接面，係在該晶圓中者；一可選擇 性设置之抗反射塗層，係在該晶圓之表面上；至少一層， 10係選擇性選自於一背面場與一鈍化層者；及導電接頭，係 位在d亥晶圓上者。 本發明之又一實施例亦提供一種太陽能電池包含： 一晶圓，係由一連續鑄態近似單晶矽體形成，且該近似單 晶矽體具有至少兩各為至少大約35cm之尺寸；一p_n接面， 15係在該晶圓中者；一可選擇性設置之抗反射塗層，係在該 晶圓之表面上；至少一層，係選擇性選自於一背面場與— 純化層者；及導電接頭，係位在該晶圓上者。 本發明之另一實施例亦提供一種晶圓，包含係由一連 續近似單晶矽體形成之矽，且該近似單晶矽體沒有或實質 20上沒有徑向分布之雜質與缺陷，並且該近似單晶矽體具有 至少兩各為至少大約25cm之尺寸及一至少大約2〇cm之第 三尺寸。 本發明之再一實施例亦提供一種晶圓，包含由一連續 鑄態近似單晶矽體形成之矽，且該晶圓具有至少一至少大 13 201229330 約為50匪之尺寸，並且該近似單晶矽體具有至少兩各為至 少大約25cm之尺寸及一至少大約20cm之第三尺寸。 本發明之又一實施例亦提供一種太陽能電池，包含： 一晶圓，係由切割一連續單晶矽體而形成者，且該單晶矽 5 體沒有或實質上沒有徑向分布之雜質與缺陷，並且該單晶 矽體具有至少兩各為至少大約25cm之尺寸及一至少大約 20cm之第三尺寸；一p-n接面，係在該晶圓中者；一可選擇 性設置之抗反射塗層，係在該晶圓之表面上；一可選擇設 置之背面場；一或多個可選擇性設置之鈍化層者；及多數 10 導電接頭，係位在該晶圓之至少一表面上者。 本發明之另一實施例亦提供一種太陽能電池，包含： 一晶圓，係由切割一連續單晶矽體而形成者，且該單晶矽 體沒有或實質上沒有徑向分布之雜質與缺陷，並且該單晶 矽體具有至少兩各為至少大約35cm之尺寸；一p-n接面，係 15 在該晶圓中者；一可選擇性設置之抗反射塗層，係在該晶 圓之表面上；一可選擇設置之背面場；一或多個可選擇性 設置之鈍化層者；及多數導電接頭，係位在該晶圓之至少 一表面上者。 本發明之再一實施例亦提供一種太陽能電池，包含： 20 —連續單晶矽晶圓，係由切割一連續單晶矽體而形成者， 且該單晶矽體沒有或實質上沒有徑向分布之雜質與缺陷， 而該晶圓具有至少一至少大約40mm之尺寸，並且該單晶矽 體具有至少兩各為至少大約25cm之尺寸及一至少大約 20cm之第三尺寸；一p-n接面，係在該晶圓中者；一可選擇 14 201229330 性設置之抗反射塗層，係在該晶圓之表面上；—可選擇設 置之背面場；一或多個可選擇性設置之鈍化層者；及多數 導電接頭，係位在該晶圓之至少一表面上者。 依據本發明之另一實施例，依據本發明製成之近似單 5晶矽可最多包含具有其他晶體方位之5%體積的較小矽晶 體。較佳地，依據本發明之再一實施例，依據本發明製成 之近似單晶矽可最多包含具有其他晶體方位之丨％體積的 較小矽晶體。更佳地，依據本發明之又一實施例，依據本 發明製成之近似單晶石夕可最多包含具有其他晶體方位之 10 0.1%體積的較小矽晶體。 本發明之其他特徵與優點將以下說明令提出，且可由 該說明了解或藉由實施本發明之實施例而明白。本發明之 特徵與其他優點可藉由在以下說明與申請專利範圍及添附 圖式中特別指出之半導體元件結構與製備方法及裝置實現 15 與獲得。 在此應了解的是前述一般性說明與以下詳細說明係舉 例與說㈣者’且欲再說明如㈣專職圍界定之本發明。 圖式簡單說明 加入並構成此說明—部份之添附圖式顯示本發明之實 20施例’且與該說明一起解釋本發明之特徵、優點與原理。 在圖式中： 第1圖顯示本發明實施例之在一坩堝底面上的一矽晶 種結構例； 第2圖顯示本發明實施例之在一坩堝底面上的另一矽 15 201229330 晶種結構例； 第3A-3C圖顯示本發明實施例之用以在一坩堝中鑄造 依幾何形狀規則排列多晶矽之鋪排（tiling)例； 第4圖顯示本發明實施例之用以在一坩堝中鑄造依幾 5 何形狀規則排列多晶矽之另一鋪排例； 第5圖顯示本發明實施例之緊密堆疊鹵晶種鋪片陣列； 第6圖顯示本發明實施例之具有斜方形或三角形格隙 之多邊形形狀的陣列例； 第7圖顯示本發明實施例之方法例；及 10 第8A-8G與9圖顯示本發明實施例之單晶矽或依幾何 形狀規則排列多晶矽之鑄造製程例。 C實施方式3 實施例之說明 以下將詳細參照本發明之實施例，且其例子係顯示於 15 添附圖式中。儘可能地，在該等圖式中使用相同或類似符 號表示相同或類似零件。 在本發明之實施例中，熔融矽之結晶係利用使用一或 多個種晶之鑄造製程來進行。如在此所揭露者，這些鑄造 製程可控制在結晶矽之鑄態體中之晶粒尺寸、形狀與方 20 位。在此所使用之用語“鑄造”表示|ί由在一用以固持熔融 矽之模具或容器中冷卻該熔融矽來形成矽者。由於如熔融 矽等液體將具有放置它之容器的形狀，所以在此亦可知在 以除了在模具或容器之任一裝置中收納該熔融矽時亦可冷 卻該熔融矽。舉例而言，該矽可以藉由在一坩堝中固化而 16 201229330 形成，此時固化係由該掛堝之至少一壁造成，且不是透過 加入該熔融物中之冷卻外來物體造成。該坩堝可以具有如 $柱形、或盒狀之任—適當形狀^如此，本發明炫融石夕結 晶之製程不是由“抽拉”一晶链或晶帶來控制。此外，依據 5本發明之實施例，該模具、容器或掛禍包括至少—心亥炼 融石夕接觸之“熱側壁”。在此所使用之用語“熱㈣一 與它接觸之炼融石夕等溫或更熱之表面，且較佳地，一熱側 壁表面在處理該石夕時是固定的。 10 15 20 '•Ί Η0 佩尽發明·^員他例，孩結晶矽可以是具有受控制 粒方位之連續單結晶或連續幾何型多結晶。在此所㈣ 用語“連續單晶矽’，表示單一結晶矽’其中該矽體是 I晶石夕且不是多數結合在—起形成_較切塊之較切 塊。此外’在此所使用之用語‘‘連續幾何型多㈣，，表 何51多晶⑦’其中财體是__均質幾何型多晶教不’ 數結合在一起形成-較大石夕塊之較小石夕塊。 夕 :據:發明之實施例’利用將一所需之結晶矽“晶種” '·'、Γ x固持㈣歡石英㈣等容ϋ底部，可 以凡成該結晶。在此所使用之用語“晶種，，表示 ^結晶體結構之具幾何雜_，且_最好 :具有-以多邊形為佳之幾何形狀，並且具有_ ^ ==的側。這晶種可—或： 而由-單晶♦之鑄塊’如—利用切割或其他方式 一曰 ' 獲侍之板片或水平段。依據本發明， 曰曰種可具有-平行於其底面之頂面，但不—定要如此。 17 201229330 5 例如…晶種可以ϋ鬼’且其尺寸可由大約2職至大約 3〇〇〇mm左右。例如，—晶種可以為大約1〇聊至大約 3〇〇mm。該石夕塊可具有大約lmm至大約_賴之厚度，且 以大約5麵至50臟為佳。1當尺寸與雜之晶種可以依 方便與麟之目的來選擇，以下將詳細說狀鋪排係石夕晶 種以-航幾何型方位或圖案配置在，例如，—㈣之底 部或者一❹個側與底面上。該晶種或該等晶種最好覆蓋 。它們所在處鄰接之整個_表面，因此當移動該具種晶 成長固化前面遠離該等晶種時，該购之全尺寸可以維持 成一致之幾何型晶體。 接著，在晶種存在之情形下使該炼融石夕冷卻與結晶， 且該炼融石夕之冷卻方式最好是可使該炫融石夕之結晶化在該 固態晶種之初始頂部高度處或以下開始並繼續遠離，且最 好疋向上遠離该等晶種。在該熔融石夕邊緣處之固-液界面最 15好在開始時與如一進行鑄造之坩堝中之表面等容器之冷卻 表面一致，依據本發明之實施例，在該熔融矽與該結合晶 之間的液-固界面可以在該鑄造製程之部份或全部令實質 上保持平坦。在本發明之實施例中，在該熔融矽之各邊緣 處的固-液界面在冷卻時受釗控制，以朝—可增加在該熔融 1〇矽與該坩堝之冷卻表面間之距離的方向移動，並最好保持 一實質平坦之固-液界面。 因此，依據本發明，该固化前面可平行於該容器之冷 部表面形狀。例如，利用〆具有平坦底部之时禍該固化 前面可仍實質保持平坦，裏該固-液界面具有—受控制之輪 201229330 廓。該固-液界面可控制成使其曲率半徑在由邊緣移動至中 心時逐漸減少，或者，該固-液界面可以控制成維持該容器 寬度至少一半的平均曲率半徑。此外，該固-液界面可以控 制成維持該容器寬度至少兩倍的平均曲率半徑。該固體可 5 具有一稍微外凸之界面且具有該容器寬度至少大約四倍的 曲率半徑，例如，該固-液界面可在一 0.7m平方坩堝中具有 一大致大於2m之曲率半徑，且大於該坩堝之水平尺寸兩 倍，並且最好大約是該坩堝之水平尺寸大約8倍至大約16 倍。 10 依據本發明之實施例，可形成最好具有至少兩各至少 大約為20cm，例如，在一側至少大約為20cm之尺寸及至少 大約10cm之第三尺寸的固態單晶矽體或近似單晶矽體，且 最好是鑄態矽體。較佳地，可形成最好具有至少兩各至少 大約為30cm，例如，在一側至少大約為30cm之尺寸及至少 15 大約10cm之第三尺寸的固態單晶矽體或近似單晶矽體，且 最好是鑄態矽體。更佳地，可形成最好具有至少兩各至少 大約為35cm，例如，在一側至少大約為35cm之尺寸及至少 大約10cm之第三尺寸的固態單晶矽體或近似單晶矽體，且 最好是鑄態矽體。最佳地，可形成最好具有至少兩各至少 20 大約為40cm，例如，在一側至少大約為40cm之尺寸及至少 大約20cm之第三尺寸的固態單晶矽體或近似單晶矽體，且 最好是鑄態矽體。又，較佳地，可形成最好具有至少兩各 至少大約為50cm，例如，在一側至少大約為50cm之尺寸及 至少大約20cm之第三尺寸的固態單晶矽體或近似單晶矽 19 201229330 體，且最好是鑄態矽體。又，更佳地，可形成最好具有至 少兩各至少大約為60cm，例如，在一側至少大約為60cm之 尺寸及至少大約20cm之第三尺寸的固態單晶矽體或近似單 晶矽體，且最好是鑄態矽體。又，最佳地，可形成最好具 5 有至少兩各至少大約為70cm，例如，在一側至少大約為 70cm之尺寸及至少大約20cm之第三尺寸的固態單晶矽體 或近似單晶矽體，且最好是鑄態矽體。依據本發明之實施 例，可形成一沒有或實質上沒有徑向分布缺陷及/或雜質且 具有至少兩各至少大約為20cm、及至少大約10cm之第三尺 10 寸的固態連續單晶矽體或近似單晶矽體。較佳地，可形成 一沒有或實質上沒有徑向分布缺陷及/或雜質且具有至少 兩各至少大約為30cm、及至少大約10cm之第三尺寸的固態 連續單晶矽體或近似單晶矽體。更佳地，可形成一沒有或 實質上沒有徑向分布缺陷及/或雜質且具有至少兩各至少 15 大約為35cm、及至少大約10cm之第三尺寸的固態連續單晶 矽體或近似單晶矽體。最佳地，可形成一沒有或實質上沒 有徑向分布缺陷及/或雜質且具有至少兩各至少大約為 40cm、及至少大約20cm之第三尺寸的固態連續單晶矽體或 近似單晶矽體。又，較佳地，可形成一沒有或實質上沒有 20 徑向分布缺陷及/或雜質且具有至少兩各至少大約為 50cm、及至少大約20cm之第三尺寸的固態連續單晶矽體或 近似單晶矽體。又，更佳地，可形成一沒有或實質上沒有 徑向分布缺陷及/或雜質且具有至少兩各至少大約為 60cm、及至少大約20cm之第三尺寸的固態連續單晶矽體或 20 201229330 近似單晶石夕體。又，最佳地’可形成一沒有或實質上沒有 徑向分布缺陷及/或雜質且具有至少兩各至少大約為 70cm、及至少大約2〇cm之第三尺寸的固態連續單晶矽體或 近似單晶矽體。 5 —依據本發明實施例製成之石夕铸塊水平尺寸的上限僅 由鑄造與坩堝製造技術來決定’而不是由發明之方法本身 來決定。依據本發明’可製備具有至少lm2且最多4·8ιη2之 橫截面積的鑄塊。類似地’該缚塊之高度上限會與較長之 循環時間有關，而非鑄造製程之基本條件。最多大約50cm 10 至大約80cm之鑄塊高度是可能的，如此，依據本發明，一 連續單晶石夕體或近似單晶矽體可以成功地成長至具有大約 6cmx66cm之;^截面’而一塊矩形固態連續單晶石夕之體積 至少為33,75〇Cm3。此外’依據本發明，鑄態連續單晶矽或 近似單晶石夕之固體可以較佳地形成具有至少兩各與-鑄造 15令器内〇P尺寸一樣大之尺寸、及-與該鑄塊高度相同之第 、 士 如果该早晶鱗石夕體是一立方體形或一矩 形固體則别述這些尺寸係指這些矽體之長度、寬度與高 度。 類似地，可形成一較佳地具有至少兩各至少大約10cm 之尺寸、及至少大約5cm之第三尺寸的铸態幾何型多晶石夕固 體較佳地，可形成一具有至少兩各至少大約20cm之尺寸、 及至v大約5cm之第三尺寸的鑄態幾何型多晶矽固體。更佳 地’可形成—具有至少兩各至少大約3Gom之尺寸、及至少 大、力5cm之第二尺寸的鑄態幾何型多晶矽固體。又，更佳 21 201229330 地，可形成一具有至少兩各至少大約35cm之尺寸、及至少 大約5cm之第三尺寸的鑄態幾何型多晶矽固體。又，較佳 地，可形成一具有至少兩各至少大約40cm之尺寸、及至少 大約5cm之第三尺寸的鑄態幾何型多晶矽固體。更佳地，可 5 形成一具有至少兩各至少大約50cm之尺寸、及至少大約 5cm之第三尺寸的鑄態幾何型多晶矽固體。又，更佳地，可 形成一具有至少兩各至少大約60cm之尺寸、及至少大約 5cm之第三尺寸的鑄態幾何型多晶石夕固體。較佳地，可形成 一具有至少兩各至少大約70cm之尺寸、及至少大約5cm之 10 第三尺寸的鑄態幾何型多晶矽固體。如此，依據本發明， 一連續單晶矽體或近似單晶矽體可以成功地成長至具有大 約66cmx66cm之橫截面，而一塊矩形固態連續單晶石夕之體 積至少為33,750cm3。此外，依據本發明，可以較佳地形成 具有至少兩各與一鑄造容器内部尺寸一樣大之尺寸、及一 15 與該鑄塊高度相同之第三尺寸的鑄態連續單晶矽固體。例 如，如果該單晶鑄態矽體是一立方體形或一矩形固體，則 前述這些尺寸係指這些矽體之長度、寬度與高度。 藉由依據本發明實施例之方式進行熔融矽之結晶化， 可製成具有特定而非任意之晶界及特定晶粒尺寸之鑄態 20 矽。此外，藉由以使所有晶種互相定向於相同相對方向之 方式來對齊該等晶種，例如，該（100)極方向垂直於該坩堝 底部且該（110)極方向平行於一矩形或正方形橫截面坩堝之 其中一側，則可得到大的鑄態矽體，且該鑄態矽體是或幾 乎是其中該鑄態矽之極方向與該（等）之極方向相同的單晶 22 201229330BRIEF DESCRIPTION OF THE INVENTION The present invention provides a method for preparing an as-cast crucible comprising: placing a molten crucible in a container to contact at least one U-stone seed crystal The container has one or more side walls of heat to at least the side wall of the glare temperature and at least one wall for cooling; and a solid crystal single crystal body formed by cooling the molten stone to control crystallization And the single crystal body may optionally have at least two dimensions of at least about 1 〇 (; 〇1, wherein the forming step includes at least initially melting the at least one of the walls for cooling 2 〇矽A solid-liquid interface is formed at the edge, and when cooled, the interface is controlled to move in a direction that increases the distance between the molten crucible and the at least-cooled wall. What is known here is One wall may be the bottom of the crucible. One embodiment of the present invention also provides a method for preparing an as-cast crucible 201229330 comprising: placing at least one of a plurality of single crystal germanium seed crystals in a geometric structure On the surface And the hanging frame has one or more side walls heated to at least the melting temperature of the stone and at least one wall for cooling, wherein the geometric structure comprises a tightly stacked polygon; and the melting crucible is placed to contact the single 5 a geometric structure of the crystal seed crystal; and a solid single crystal body formed by cooling the molten crucible to control crystallization, and the single crystal body selectively has at least two sizes each of at least about 10 cm. Wherein the forming step comprises forming a solid-liquid interface at least initially at the edge of the molten crucible of the at least one wall for cooling, and upon cooling, the interface is controlled to increase the melting crucible and the at least one The embodiment of the present invention also provides a method for preparing an as-cast crucible, comprising: arranging a plurality of single crystal germanium seed crystals in at least one predetermined pattern in a predetermined pattern. On both surfaces; placing the molten crucible to contact the single crystal 15; and cooling the molten crucible from at least two surfaces of the crucible to control crystallization to form a solid a single crystal body, and the single crystal body selectively has at least two dimensions each of at least about 10 cm, wherein the forming step comprises controlling a solid-liquid interface at the edge of the melting crucible upon cooling to bring it to a A direction 20 in which the distance between the molten crucible and at least two surfaces of the crucible can be increased. A further embodiment of the present invention also provides a method for preparing an as-cast crucible comprising: placing a crucible feed to contact it At least one single crystal germanium seed crystal on at least one surface; heating the germanium feed and the at least one single crystal germanium seed crystal to a melting temperature of the crucible; controlling the heating so that the at least one single crystal germanium seed crystal does not 8 201229330 70 king melts and "Hai control contains maintenance. When another point in the 到达 arrives at the UU, 1 Τ Τ is approximately equal to or less than 0.1 C/min when measured on the surface of the powder. A single crystal germanium seed crystal partially melts 'a solid crystal single crystal body by cooling the crucible. A further embodiment of the present month also provides a method for preparing an as-cast stone stalk L3, which is to place a geometric structure of a single crystal 矽 seed crystal on a V 纟 surface, where the geometric structure Including a closely-stacked polygon, placing 6 haishi eve feed to contact the at least one of the aforementioned single crystal saplings on the at least surface; heating the shi shi feed and the plurality of single crystal slabs to the stone The melting temperature of eve 10; controlling the heating so that the majority of the single crystals of the single crystal are not melted by the king's and the 5th control is maintained until the other temperature reaches the tempering temperature, When the silk surface is averaged, the enthalpy is equal to or less than O.PC/min; and - at least the above-mentioned single crystal (tetra) crystal is partially refining, and the solid crystallization of the ruthenium is formed by cooling the ruthenium. Further, the embodiment of the invention provides a method for preparing a squamous stone stalk, which comprises arranging a plurality of single crystal saplings on at least two surfaces of a catastrophe in a predetermined pattern; Feeding, contacting a plurality of single crystals on the at least two surfaces; heating the daylight feed and the melting temperature of the plurality of the emeralds to the stone eve; controlling the heating to make the majority The single crystal sapphire 2 twins will not completely melt, and the control will be maintained. When the melting temperature is reached at another point in the series, the enthalpy at the outer surface is approximately equal to or less than G.TOmin. And - at least - the single crystal (tetra) crystal is partially melted, and the solid crystal single crystal body is formed by cooling the crucible. A further embodiment of the present invention also provides a method for preparing a prayer state, the method of 201229330, comprising: placing a molten crucible in a container to contact at least one seed crystal, and the container has one or more heating To at least the sidewall of the melting temperature of the crucible, and the at least one seed crystal is configured to cover the entire or substantially the entire area of the surface of the vessel; and to form a solid single crystal by cooling the molten crucible to control crystallization A steroid, and the single crystal steroid may optionally have at least two dimensions each of at least about 1 〇cm. Yet another embodiment of the present invention also provides a continuous single crystal body having no or substantially no radially distributed impurities and defects and having at least two of at least about 25 cm in size and at least about The third size of 20cm 10 . Another embodiment of the present invention also provides a continuous single crystal body, and the single crystal body has a carbon concentration of about 2×10 016 atoms/cm 3 to 5×10 17 atoms/cm 3 , an oxygen wave of no more than 5×10 017 atoms/cm 3 , at least l×l 015 atoms/cm 3 . The nitrogen concentration and has at least two dimensions each of at least about 15 25 cm and a third dimension of at least about 20 cm. Yet another embodiment of the present invention also provides a continuous as-cast single crystal body having at least two dimensions each of at least about 35 cm. A further embodiment of the present invention also provides a solar cell comprising: a wafer formed of a continuous single crystal body, and the single crystal body has no or substantially no radial distribution of impurities and defects, and The single crystal body has at least two dimensions each of at least about 25 cm in size and a third dimension of at least about 20 cm; a pn junction in the wafer; an optional anti-reflective coating, On the surface of the wafer; at least one layer is selectively selected from a back surface field and a purification layer; and a conductive 10 201229330 connector is attached to the wafer. Another embodiment of the present invention also provides a solar cell comprising: a wafer formed of a continuous as-cast single crystal body, and the single crystal body having at least two sizes of at least about 35 Å; _ρ_η a junction, in the wafer; an optional anti-reflective coating on the surface of the wafer; at least one layer selectively selected from a back surface field and a passivation layer; The conductive joint ' is positioned on the wafer. A further embodiment of the present invention also provides a solar cell comprising: a continuous single crystal germanium wafer formed by a continuous as-cast single crystal germanium, and the 10 wafers having at least one size of at least about 50 mm And the single crystal body has at least two dimensions each of at least about 25 cm in size and at least about 2 〇 cm; a p_n junction in the wafer; an optional anti-reflection The coating is on the surface of the wafer; at least one layer is selectively selected from a back surface field and a passivation layer; and a conductive joint is placed on the wafer. Another embodiment of the present invention also provides a wafer comprising a crucible formed of a continuous single crystal germanium, and the single crystal germanium has no or substantially no radially distributed impurities and defects, and the single crystal germanium The body has at least two dimensions each of at least about 25 cm in size and a third dimension of at least about 2 cm. A further embodiment of the present invention also provides a wafer comprising a crucible formed of a continuous single crystal germanium, and the wafer has at least one size of at least about 5 Å, and the single crystal corpus has at least two Each is a size of at least about 25 inches and a third size of at least about 2 inches. A consistent embodiment of the present invention also provides a method for preparing as-cast stone eves 201229330 = 'contains: arranging and immersing in the container' to make it contact with at least one stone day and day with one or more Heating to at least the u-wall of the melting temperature of the crucible and at least - a wall for cooling; and forming a solid near-crystal single crystal body by cooling the solution (four) to control crystallization, and the approximate single crystal body can be 5 Optionally having at least two dimensions each of at least about 1 〇cm, wherein the forming step includes forming a solid-liquid interface at least initially at the edge of the at least one of the walls for cooling, and cooling The interface is controlled to move in a direction that increases the distance between the molten crucible and the at least one wall for cooling. Another embodiment of the present invention also provides a method for preparing an as-cast crucible, comprising: placing a molten crucible in a container to contact at least one of the crucibles and having one or more Heating to at least the sidewall of the glare temperature of the stone, and the at least one seed crystal is configured to cover the entire or substantially the entire area of the surface of the container; and forming a solid by cooling the molten crucible to control crystallization The single crystal body is approximately, and the single crystal body may optionally have at least two dimensions each of at least about 10 cm. Yet another embodiment of the present invention also provides a continuous approximation of a single crystal body, and the substantially single crystal body has no or substantially no radial distribution of impurities and I5»' and has at least two of at least about 25 cm each. The size and a third dimension of at least 20 and about 20 cm. Another embodiment of the present disclosure also provides a continuous approximation of a single crystal stone body, and the approximate early crystal body has a carbon concentration of about 2 x 10 16 atoms/cm 3 to 5 x 10 17 atoms/cm 3 , an oxygen concentration of no more than 5 x 1 017 atoms / cm 3 , at least l x l Ol 5 atoms / The nitrogen concentration of cm3, and having at least two dimensions of 12 201229330 of at least about 25 cm and a third dimension of at least about 2 ounces. Still further embodiments of the present invention also provide a continuous approximation of a single crystal stone body, and the approximate single crystal stone body has at least two of at least about a set size. A further embodiment of the present invention also provides a solar cell comprising: 5 a wafer formed by a continuous approximate single crystal body, and the substantially single crystal body has no or substantially no radial distribution of impurities and defects And the single crystal stone body has at least two dimensions each having a size of at least about 25 cm and a thickness of at least about 20 cm; a ρ·η junction, which is in the wafer; and an optionally settable resistance The reflective coating is on the surface of the wafer; at least one layer, the 10 series is selectively selected from a back surface field and a passivation layer; and the conductive joint is tied to the wafer. A further embodiment of the present invention also provides a solar cell comprising: a wafer formed by a continuous as-cast approximately single crystal body, and the approximately single crystal body having at least two dimensions each of at least about 35 cm; a p_n junction, 15 is in the wafer; an optional anti-reflective coating is on the surface of the wafer; at least one layer is selectively selected from a back surface field and a purification layer And a conductive joint that is tied to the wafer. Another embodiment of the present invention also provides a wafer comprising a crucible formed by a continuous approximate single crystal germanium, and the substantially single crystal germanium has no or substantially no radial distribution of impurities and defects thereon, and the The substantially single crystal body has at least two dimensions each of at least about 25 cm in size and a third dimension of at least about 2 〇 cm. A further embodiment of the present invention also provides a wafer comprising a crucible formed of a continuous as-cast approximately single crystal body, and the wafer has a size of at least one at least 13 201229330 of about 50 Å, and the approximate single The wafer body has at least two dimensions each of at least about 25 cm in size and a third dimension of at least about 20 cm. A further embodiment of the present invention also provides a solar cell comprising: a wafer formed by cutting a continuous single crystal body, and the single crystal germanium body 5 has no or substantially no radial distribution of impurities and a defect, and the single crystal body has at least two dimensions each of at least about 25 cm in size and a third dimension of at least about 20 cm; a pn junction in the wafer; an optional anti-reflective coating a layer on the surface of the wafer; an optional back surface field; one or more selectively disposed passivation layers; and a plurality of 10 conductive contacts on the at least one surface of the wafer . Another embodiment of the present invention also provides a solar cell comprising: a wafer formed by cutting a continuous single crystal body, and the single crystal body has no or substantially no radial distribution of impurities and defects And the single crystal body has at least two dimensions each of at least about 35 cm; a pn junction, in the wafer; an optional anti-reflective coating on the surface of the wafer An optional back surface field; one or more selectively disposed passivation layers; and a plurality of electrically conductive contacts that are positioned on at least one surface of the wafer. A further embodiment of the present invention also provides a solar cell comprising: 20 - a continuous single crystal germanium wafer formed by cutting a continuous single crystal germanium body, and the single crystal germanium body has no or substantially no radial direction Distributing impurities and defects, and the wafer has at least one dimension of at least about 40 mm, and the single crystal body has at least two dimensions each of at least about 25 cm and a third dimension of at least about 20 cm; a pn junction, Attached to the wafer; an optional 14 201229330 anti-reflective coating on the surface of the wafer; - optional back surface field; one or more selectively set passivation layers And a plurality of conductive joints that are tied to at least one surface of the wafer. In accordance with another embodiment of the present invention, an approximately single crystal wafer made in accordance with the present invention may comprise up to 5% by volume of smaller germanium crystals having other crystal orientations. Preferably, in accordance with still another embodiment of the present invention, an approximately single crystal germanium fabricated in accordance with the present invention may comprise at most a smaller germanium crystal having a volume of other crystal orientations of 丨%. More preferably, in accordance with yet another embodiment of the present invention, an approximately single crystal stone made in accordance with the present invention may comprise up to 0.1% by volume of smaller germanium crystals having other crystal orientations. Other features and advantages of the invention will be set forth in the description which follows. The features and other advantages of the present invention can be obtained and obtained by the semiconductor device structure and preparation method and apparatus specifically indicated in the following description and the appended claims. It is to be understood that the foregoing general description and the following detailed description of the invention and claims BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in FIG In the drawings: Fig. 1 shows an example of a seed crystal structure on a bottom surface of an embodiment of the present invention; Fig. 2 shows another crucible 15 201229330 seed crystal structure on a bottom surface of an embodiment of the present invention. Example 3A-3C shows an example of tiling in which a polycrystalline crucible is regularly arranged in a crucible in a crucible according to an embodiment of the present invention; and FIG. 4 shows an embodiment of the embodiment of the present invention for casting in a crucible. Another layout example of a polycrystalline crucible arranged in a regular manner; FIG. 5 shows a closely packed halogen seed patch array according to an embodiment of the present invention; and FIG. 6 shows a polygonal shape having a rhombic or triangular gap in an embodiment of the present invention. Example of the array; Fig. 7 shows an example of the method of the embodiment of the present invention; and 10 Figs. 8A-8G and 9 show an example of a casting process in which a single crystal germanium or a polycrystalline germanium is regularly arranged according to the geometrical shape of the embodiment of the present invention. C. Embodiment 3 Description of Embodiments Reference will now be made in detail to the embodiments of the invention, Wherever possible, the same or similar symbols are used in the drawings to refer to the same or similar parts. In an embodiment of the invention, the crystallization of the molten ruthenium is carried out using a casting process using one or more seed crystals. As disclosed herein, these casting processes control the grain size, shape, and orientation of the crystalline body in the as-cast body. The term "casting" as used herein means that the crucible is formed by cooling the molten crucible in a mold or container for holding the molten crucible. Since the liquid such as molten helium will have the shape of the container in which it is placed, it is also known here that the molten crucible can be cooled even when the molten crucible is accommodated in any of the molds or containers. For example, the crucible can be formed by curing in a crucible 16 201229330, where the curing is caused by at least one wall of the peg and not by cooling foreign objects added to the melt. The crucible may have any shape such as a columnar shape or a box shape. Thus, the process of the present invention is not controlled by "drawing" a crystal chain or a crystal ribbon. Further, according to an embodiment of the present invention, the mold, the container or the catastrophe includes at least a "hot side wall" of the contact of the core. As used herein, the term "hot (4) - a surface of a smelting stone in contact with it is isothermally or hotter, and preferably, a hot sidewall surface is fixed when the stone is treated. 10 15 20 '• Ί Η 0 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 佩 彼 彼 彼 彼 彼 彼 彼 彼 彼 彼 彼 彼 彼 彼 彼 彼 彼 彼The carcass is I-Crystal and not the majority of the cleavage. In addition, 'the term used here' is continuous geometric type (four), and the table is 51 polycrystalline 7' where the financial body is __homogeneous geometric polycrystalline teaching is not combined with the number - the larger stone occlusion Xiaoshi Xi block. On the eve: According to the embodiment of the invention, the crystals can be formed by using a desired crystal crystallization "seed" "·", Γ x holding (4) quartz crystal (four), and the like. As used herein, the term "seed," means that the crystal structure has a geometrical _, and _ preferably: has a geometry that is preferably a polygon, and has a side of _ ^ ==. This seed can be - or : and the ingot of the single crystal ♦ 'for a sheet or horizontal section obtained by cutting or otherwise plucking. According to the invention, the seed may have a top surface parallel to the bottom surface thereof, but not - This is the case. 17 201229330 5 For example, the seed crystal can be smashed and its size can be from about 2 to about 3 〇〇〇 mm. For example, the seed crystal can be about 1 〇 to about 3 〇〇 mm. The stone block may have a thickness of about 1 mm to about _, and preferably about 5 to 50. 1 When the size and the seed crystal can be selected according to the purpose of convenience, the following will be described in detail. The seed crystals are arranged in a geometrical orientation or pattern, for example, at the bottom of the - (4) or on one side and the bottom surface. The seed crystal or the seed crystals are preferably covered. a surface, so when moving the seed crystal growth curing front away from the seed crystals, The full size can be maintained as a uniform geometric crystal. Then, in the presence of the seed crystal, the smelting stone is cooled and crystallized, and the cooling method of the smelting stone is preferably made by the smelting The crystallization begins at the initial top height of the solid seed crystal or below and continues away, and preferably upwards away from the seed crystals. The solid-liquid interface at the edge of the molten stone is at the beginning of the 15 If the cooling surface of the container such as the surface of the casting is uniform, according to an embodiment of the present invention, the liquid-solid interface between the molten crucible and the bonding crystal may be substantially or partially in the casting process. Keeping flat. In an embodiment of the invention, the solid-liquid interface at each edge of the molten crucible is controlled by the crucible during cooling to increase between the molten crucible and the cooling surface of the crucible The direction of the distance moves and preferably maintains a substantially flat solid-liquid interface. Thus, in accordance with the present invention, the solidified front can be parallel to the shape of the cold surface of the container. For example, when the crucible has a flat bottom, The solidified front can still remain substantially flat, and the solid-liquid interface has a controlled wheel 201229330. The solid-liquid interface can be controlled such that its radius of curvature gradually decreases from edge to center, or the solid The liquid interface can be controlled to maintain an average radius of curvature of at least half of the width of the container. Further, the solid-liquid interface can be controlled to maintain an average radius of curvature of at least twice the width of the container. The solid 5 can have a slightly convex interface and Having a radius of curvature of at least about four times the width of the container, for example, the solid-liquid interface may have a radius of curvature of substantially greater than 2 m in a 0.7 m square inch and greater than twice the horizontal dimension of the crucible, and preferably about Preferably, the horizontal dimension of the crucible is from about 8 to about 16 times. 10 In accordance with an embodiment of the present invention, it may be formed to have at least two at least about 20 cm each, for example, at least about 20 cm on one side and at least about 10 cm. The third size solid single crystal body or approximately single crystal body, and preferably the as-cast body. Preferably, a solid single crystal body or an approximately single crystal body having at least two at least about 30 cm each, for example, a size of at least about 30 cm on one side and a third size of at least 15 cm of about 10 cm, is formed. And it is preferably an as-cast body. More preferably, a solid single crystal body or an approximately single crystal body preferably having at least two at least about 35 cm each, for example, a size of at least about 35 cm on one side and a third size of at least about 10 cm, and It is best to cast the body. Most preferably, a solid single crystal body or an approximately single crystal body preferably having at least two at least 20 each of about 40 cm, for example, a size of at least about 40 cm on one side and a third size of at least about 20 cm, And it is preferably an as-cast body. Further, preferably, a solid single crystal body or an approximately single crystal crucible having at least two at least about 50 cm each, for example, a size of at least about 50 cm on one side and a third size of at least about 20 cm may be formed. 201229330 Body, and preferably cast as carcass. Still more preferably, a solid single crystal body or an approximately single crystal body preferably having at least two at least about 60 cm each, for example, a size of at least about 60 cm on one side and a third size of at least about 20 cm. And preferably the as-cast body. Also, optimally, a solid single crystal body or substantially single crystal having at least two at least about 70 cm each, for example, a size of at least about 70 cm on one side and a third size of at least about 20 cm may be formed. Carcass, and preferably cast as carcass. In accordance with an embodiment of the present invention, a solid continuous single crystal corpus callosum having no or substantially no radial distribution defects and/or impurities and having at least two third tens of 10 inches each at least about 20 cm and at least about 10 cm can be formed. Or approximate single crystal corpus callosum. Preferably, a solid continuous single crystal body or approximately single crystal germanium having no or substantially no radial distribution defects and/or impurities and having at least two third dimensions each of at least about 30 cm and at least about 10 cm can be formed. body. More preferably, a solid continuous single crystal body or substantially single crystal having at least two third dimensions of at least about 35 cm and at least about 10 cm each having no or substantially no radial distribution defects and/or impurities may be formed. Carcass. Most preferably, a solid continuous single crystal corpus or approximately single crystal enthalpy having no or substantially no radial distribution defects and/or impurities and having at least two third dimensions each of at least about 40 cm and at least about 20 cm can be formed. body. Moreover, preferably, a solid continuous single crystal body or approximation having at least two radial distribution defects and/or impurities and having at least two third dimensions each of at least about 50 cm and at least about 20 cm can be formed. Single crystal corpus callosum. Further, more preferably, a solid continuous single crystal body having no or substantially no radial distribution defects and/or impurities and having at least two third dimensions each of at least about 60 cm and at least about 20 cm can be formed or 20 201229330 Approximate single crystal stone body. Also, preferably, a solid continuous single crystal body having no or substantially no radial distribution defects and/or impurities and having at least two third dimensions each of at least about 70 cm and at least about 2 〇cm may be formed or Approximately single crystal corpus callosum. 5 - The upper limit of the horizontal dimension of the Shixi ingot made in accordance with an embodiment of the present invention is determined solely by the casting and niobium manufacturing techniques, rather than by the method of the invention itself. According to the present invention, an ingot having a cross-sectional area of at least lm2 and at most 4·8 ηη 2 can be prepared. Similarly, the upper limit of the height of the block is related to a longer cycle time than the basic condition of the casting process. An ingot height of up to about 50 cm 10 to about 80 cm is possible, and thus, according to the present invention, a continuous single crystal stone or an approximately single crystal body can be successfully grown to have a shape of about 6 cm x 66 cm; The solid continuous single crystal stone has a volume of at least 33,75 〇Cm3. Further, in accordance with the present invention, an as-cast continuous single crystal crucible or an approximately single crystal solid may preferably be formed to have at least two dimensions that are as large as the size of the inner crucible P, and - with the ingot If the early squama is a cubic or a rectangular solid, the dimensions refer to the length, width and height of the corpses. Similarly, it is preferred to form an as-cast geometry polycrystalline fine solid having at least two dimensions each of at least about 10 cm and a third dimension of at least about 5 cm. Preferably, at least two of each have at least about An as-cast geometric polycrystalline solid of a size of 20 cm and a third dimension of v of about 5 cm. More preferably, it can be formed as an as-cast geomorphic polycrystalline solid having at least two dimensions each having a size of at least about 3 Gom and a second dimension of at least 5 cm. Further, more preferably, 21 201229330, an as-cast geometric polycrystalline solid having at least two dimensions each having a size of at least about 35 cm and a third dimension of at least about 5 cm can be formed. Still preferably, an as-cast geomorphic polycrystalline solid having at least two dimensions of at least about 40 cm each and a third dimension of at least about 5 cm can be formed. More preferably, an as-cast geomorphic polycrystalline solid having at least two dimensions each having a size of at least about 50 cm and a third dimension of at least about 5 cm is formed. Still more preferably, an as-cast geometry polycrystalline solid having at least two dimensions of at least about 60 cm each and a third dimension of at least about 5 cm can be formed. Preferably, an as-cast geometry polycrystalline solid having at least two dimensions of at least about 70 cm each and at least a third dimension of at least about 5 cm can be formed. Thus, in accordance with the present invention, a continuous single crystal body or an approximately single crystal body can be successfully grown to have a cross section of about 66 cm x 66 cm, while a rectangular solid continuous single crystal body has a volume of at least 33,750 cm3. Further, in accordance with the present invention, it is preferred to form an as-cast continuous single crystal tantalum solid having at least two dimensions each of the same size as the inner dimensions of a casting vessel and a third dimension of the same height as the ingot. For example, if the single crystal as-cast body is a cubic or a rectangular solid, the aforementioned dimensions refer to the length, width and height of the bodies. By performing crystallization of the molten crucible in accordance with an embodiment of the present invention, an as-cast state 20 having a specific and not arbitrary grain boundary and a specific grain size can be produced. Furthermore, the seed crystals are aligned by aligning all of the seed crystals in the same relative direction, for example, the (100) pole direction is perpendicular to the bottom of the crucible and the (110) pole direction is parallel to a rectangle or square. On one side of the cross-section 坩埚, a large as-cast corpus can be obtained, and the as-cast steroid is or almost a single crystal in which the pole direction of the as-cast enthalpy is the same as the pole direction of the (etc.) 201229330
Ul地其他極方向可以垂直於該坩堝之底部。此外， 之實施例，該(等)晶種可以排列成使有共同極方 向垂直於該坩堝之底部。 當單晶石夕係利用如CZWZ法等習知方法，由—池溶融 石夕中拉出-圓柱形晶㈣製成時，所得到之單晶石夕含奸 陷’例如，旋渦缺陷(由如空位與自格隙原 子專内在缺陷形成者)與⑽環缺陷及。這些旋渦缺陷可以 利用X射線圖像測得且在财中係以“旋渦，，呈現， 可在優先酸㈣使輪廓出現後，再偵測它們。 10 15 20 依據習知CZ或FZ法，在石夕内之氧原子與在該石夕中由這 陷的分布是在徑向上。這表示它們會排 列成衣狀、螺旋狀或以—中心軸為^對稱之條紋狀着 環缺陷係—種特例，其中奈米級氧沈澱在-拉出之石夕單曰 聽或晶枉内之圓柱形帶中集結生成堆疊缺陷，而在優先 酸敍後於顿品巾可讀察到這些圓柱形帶。 旋渦缺陷與0SF環缺陷兩者均會由於拉出 /法而由—池熔融雜㈣㈣Μ之單晶石夕曰 =右相反地，由本發明實施例之鑄造製程所製成之 不會有㈣旋渦缺陷與⑽環缺陷。這是因 „之韻中、及在整個固化與冷卻過程中整 =溫線大致平坦之製財，在鑄造過程中產生之缺陷大 部伤會在任意地分布在成長界面處而不會_轉影響。 有關在由不同方法長成之石夕中的輕元素雜質漠度，在 23 201229330 表1中所示之以下級數係一般考慮之特性值。 表1 濃度(atoms/cmj) 氧 碳 氮 浮動區 <lxl〇16 <1χ1016 <lxl〇14 Czochralski 2xl017-lxl〇18 <1χ1016 鑄造 2-3xl〇17 2x10 丨 6-5χ1017 >lxl〇15 CZ鑄塊之部份可以低至5xl〇17atoms/cm3之氧來製造， 但不能再低。碳與氮濃度可以在F Z與C Z鑄塊中利用刻意摻 5 雜來增加，但摻雜不會超過在這些方法中之固體溶解極限 (如同它在鑄造材料中一般），且業經摻雜之鑄塊製成之尺寸 直徑不會大於20cm。相反地，鑄塊通常會由於脫離塗層與 爐熱區之設計而以碳與氮過飽和。因此，由於液相成核作 用與成長’沈澱之氮化物與碳化物分布於各處。此外，依 10據本發明之實施例，製成之鑄態單晶塊具有前述雜質級數 且具有50x50x20cm3與60x60x5cm3之尺寸。這些尺寸僅是舉 例’且不應視為本發明鑄造製程之上限。 例如，在雜質級數方面，在依據本發明鑄造之矽中較 佳的是大約1-5x1017atoms/cm3之溶解碳濃度、大約 15 2-3 X1017at〇ms/cm3之溶解氧濃度、及 i _5 χ! 〇i5at〇ms/cm3之溶 解碳濃度。依據本發明之實施例，可形成最好具有至少兩 各至少大約為20cm，例如，在一侧至少大約為2〇cm之尺寸 及至少大約10cm之第三尺寸，並且具有大約 l-5xl017at〇mS/cm3之溶解碳濃度、大約2-3xl〇17at〇ms/cm3 20之溶解氧濃度、及1_5xl〇l5atoms/cm3之溶解碳濃度的固態 單晶石夕體或近似單晶石夕體，且最好是鑄態矽體。較佳地， 24 201229330 可形成具有至少兩各至少大約為3 0cm，例如，在一側至少 大約30cm之尺寸及至少大約i〇cm之第三尺寸，並且具有大 約 l-5xl017atoms/cm3之溶解碳濃度、大約2-3xl017atoms/cm3 之溶解氧濃度、及1-5x1015atoms/cm3之溶解碳濃度的固態 5單晶矽體或近似單晶矽體，且最好是鑄態矽體。更佳地， 可形成具有至少兩各至少大約為35cm，例如，在一側至少 大約35cm之尺寸及至少大約i〇cm之第三尺寸，並且具有大 約 1 -5X1017atoms/cm3之溶解碳濃度、大約 2-3X1017atoms/cm3 之溶解氧濃度、及l-5xlOl5atoms/cm3之溶解破濃度的固態 10 單晶矽體或近似單晶矽體，且最好是鑄態矽體。又，更佳 地，可形成具有至少兩各至少大約為40cm，例如，在一側 至少大約40cm之尺寸及至少大約20cm之第三尺寸，並且具 有大約l-5xl017atoms/cm3之溶解碳濃度、大約 2-3x10 atoms/cm3之溶解氧濃度、及l-5xl〇15atoms/cm3之溶 15 解碳濃度的固態單晶矽體或近似單晶矽體，且最好是鑄態 矽體。又，更佳地，可形成具有至少兩各至少大約為50cm， 例如’在一側至少大約50cm之尺寸及至少大約2〇cm之第三 尺寸，並且具有大約l-5xlOnatoms/cm3之溶解碳濃度、大 約 2-3xl〇17atoms/cm3之溶解氧濃度、及 i_5xl〇i5at〇ms/cm3 20 之溶解碳濃度的固態單晶矽體或近似單晶矽體，且最好是 鑄態矽體。又’更佳地，可形成具有至少兩各至少大約為 60cm，例如，在一側至少大約60cm之尺寸及至少大約20cm 之第三尺寸，並且具有大約l-5xl017atoms/cm3之溶解碳濃 度、大約2-3xl017atoms/cm3之溶解氧濃度、及 25 201229330 l-5xl015atoms/cm3之溶解碳濃度的固態單晶矽體或近似單 晶矽體，且最好是鑄態矽體。又，更佳地，玎形成具有至 少兩各至少大約為70cm，例如，在一側至少大約70cm之尺 寸及至少大約20cm之第三尺寸，並且具有大約 5 l-5xl017atoms/cm3之溶解碳濃度、大約 2-3xl〇17atoms/cm3 之溶解氧濃度、及l-5xl〇15atoms/cm3之溶解碳濃度的固態 單晶矽體或近似單晶矽體，且最好是鑄態矽體。 依據本發明之實施例，可形成一沒有或實質上沒有徑 向分布缺陷及/或雜質且具有至少兩各至少大約為2〇cm之 10 尺寸及至少大約10cm之第三尺寸，姐且具有大約 l-5xlOl7atoms/cm3之溶解碳濃度、大約2-3xl〇17atoms/cm3 之溶解氧濃度、及l-5xl〇l5at〇ms/cm3之溶解碳濃度的連續 單晶石夕體或近似單晶>5夕體。較佳地，可形成一沒有或貫質 上沒有徑向分布缺陷及/或雜質且具有至少雨各至少大約 15為3〇cm之尺寸及至少大約1〇cm之第三尺寸，迆且具有大約 l-5xlOl7atoms/cm3之溶解碳濃度、大約2-3xiq1 atoms/cm3 之溶解氧濃度、及l-5xl〇15at〇ms/cm3之溶解碳濃度的連續 單晶石夕體或近似單晶石夕體。更佳地，y形成一沒有或貫為 上沒有徑向分布缺陷及/或雜質且具有至少雨各至少大約 20為35cm之尺寸及至少大約i〇cm之第三尺寸，I且具有大約 l-5xlOl7atoms/cm3 之溶解碳濃度、大約 2_3xl017at〇mS/Cm3 之溶解氧濃度、及l-5xl〇i5atoms/cm3之溶解碳濃度的連續 單晶石夕體或近似單晶石夕體。又，更佳地，·^形成一/又有或 貫質上沒有徑向分布缺陷及/或雜質立具有至少兩各至少 26 201229330 大約為40cm之尺寸及至少大約2〇cm之第三尺寸，並且具有 大約l-5xl017atoms/cm3之溶解碳濃度、大約 2-3xl017atoms/cm3之溶解氧濃度、及udo丨5atorns/cm3之溶 解碳濃度的連續單晶石夕體或近似單晶石夕體。又，更佳地， 5可形成一沒有或實質上沒有徑向分布缺陷及/或雜質且具 有至少兩各至少大約為50cm之尺寸及至少大約20cm之第 三尺寸，並且具有大約l-5xl017atoms/cm3之溶解碳濃度、 大約2-3xlOl7atoms/cm3之溶解氧濃度、及i-5xl015atoms/cm3 之溶解碳濃度的連續單晶矽體或近似單晶矽體。又，更佳 10 地，可形成一沒有或實質上沒有徑向分布缺陷及/或雜質且 具有至少兩各至少大約為60cm之尺寸及至少大約20cm之 第三尺寸’並且具有大約l-5xl017atoms/cm3之溶解碳濃 度、大約2-3xl017atoms/cm3之溶解氧濃度、及 1 -5 X1015atoms/cm3之溶解碳濃度的連續單晶矽體或近似單 15 晶矽體。又，更佳地，可形成一沒有或實質上沒有徑向分 布缺陷及/或雜質且具有至少兩各至少大約為7〇cm之尺寸 及至少大約20cm之第三尺寸，並且具有大約 1-5x1017atoms/cm3之溶解碳濃度、大約2-3xl017at〇ms/cin3 之溶解氧濃度、及l-5xl015atoms/cm3之溶解碳濃度的連續 20 單晶矽體或近似單晶矽體。 一依據本發明實施例製成且具有前述雜質濃度之石夕鱗 塊水平尺寸的上限僅由鑄造與坩堝製造技術來決定，而不 是由發明之方法本身來決定。如此，一具有前述雜質濃度 之鎮態連續早晶碎或近似早晶珍之固體可以較佳地形成且 27 201229330 有至少兩各與一鑄造容器内 該鑄塊高度相同之第三尺寸寸一樣大之尺寸、及一與 是—立方體形或-矩形固體，ί;如果該單晶鑄態石夕體 俨夕且ώ 艰則别述這些尺寸係指這些矽 肢疋長度、寬度與高度。 10 15 20 有任㈣^發明之實施例，轉造過程中所使狀晶種可具 塊，戈^尺寸與純’且係具有適钱何雜之單晶石夕 :依，副排列之多晶妙，如正方形、矩形、 因二邊形之錢。它們可成形為便於鋪排， 邊對邊地玫置或‘‘舖排，，並以-預定圖案配合 玫置^ 此外’依據本發明之實施例，多數晶種可 =㈣包括所有之-或多側上。藉由將-如㈣ =趣專結晶㈣㈣成多數具有所“狀之塊狀，可以 t這些晶種。這些晶種亦可以藉由將它們由—利用本發 月貫施例方法製成之連續單晶或連續幾何型多晶狀樣品 刀割出來而形成’使隨後之鑄造製程中所使用之晶種可由 —初始鑄造製程製成。為了進行單晶料，最好使儘可能 少之晶種覆蓋紐财部，以避免出現缺陷。如此，該石夕 或該等科以具有其中放置_或該等心進行本發明之 縳造方法之關或其他m部等之1多側的尺寸與 形狀，或大致之尺寸與形狀。 以下將說明本發明實施狀心製切的方法及裝 置。但是，在此應了解的是這些不是形成與本發明原理相 符之矽的唯一方式。 ’ &_0«在_如石英_等具有底 28 201229330 部與壁部之坩堝底面處，使它們朝相同方位緊密抵接且形 成一大而連續定向之板片120，或者，它們以一預設錯向緊 密抵接’以在所產生之所得矽中產生具有刻意選擇之晶粒 尺寸的特定晶界。即，為鑄造幾何型多晶矽，所得之結晶 5 化幾何型多晶矽的晶粒尺寸將等於或將大約為該等晶種之 尺寸。較佳地’多數晶種100係鋪排且放置成可實質地覆蓋 坩堝110之整個底部。又，較佳地，該坩堝丨10具有一如由 氧化矽、氮化矽或一液體膠囊等製成之脫離塗層，以便將 結晶化之矽由坩堝110取出。此外，該等晶種可包含具有所 需Ba體方位之單晶石夕’且厚度為大約3mm至大約lOOmni的 一板片或多數板片。雖然在第1圖中顯示的是一特定數目與 尺寸之晶種100 ’但是發明所屬技術領域中具有通常知識者 可輕易了解該等晶種之數目與尺寸可以依據應用而增加或 減少。 15 請參閱第2圖，晶種100亦可放置在該坩堝110之一或多 個側壁130、140上。晶種1〇〇可以放置在坩堝11〇之所有四 個壁上，但為了方便說明，僅在側壁13〇、14〇上顯示晶種 100。較佳地，放置在該坩堝110四壁之任—壁上的晶種1〇〇 呈柱狀，以便進行晶體成長。較佳地，放置在該坩堝四 20壁之任一壁上之各柱狀晶種將具有與放置在它正下方且在 坩堝110底部上之晶種相同的晶粒方位。當幾何型多晶矽成 長時，依此方式放置該柱狀晶種將有助於該等幾何型矽晶 粒成長到與該坩堝110之高度一般大。 仍請參閱第2圖，這種晶種100結構之優點是—用以鑄 29 201229330 造具有更高結晶性與更高成長速度 行的方法。例如，可在__由杯，，^、、更簡單、自進 由許多堆疊在-起以在增堝丨_侧形且該石夕“杯” 5 10 15 之凹穴的晶種。或者，可將溶融⑽人1如底部與四壁 石夕“杯”由許多堆疊在—起以在__^杯”中’且該 與四壁之凹六的晶種。在另一例中，-如底部 至石夕之炼化溫度，且保持在固體狀態 禮納杯”上升 入且使之達到熱平衡1後，在前述=雜融砂倒 110冷卻，藉此，利關如__使熱軸至大氣中轨將相禍 至掛禍110開口頂部之固體散熱材料（圖未示)且熱仍可施加 底部與側部散熱。依此方式，所得之 &掛尚110 可以是單結晶 或幾何型多晶（依所使用之晶種100與其方位而6)且，妒 晶化進行之速度大於已知多晶鑄造製程。為^重覆ϋ 程，利用已知方法移除該結晶化矽塊之側邊與底部的一部 份。較佳地，多數如晶種100之種晶係排列成使在晶種1〇() 間之共同極方向垂直於坩堝110之底部與一側部的各部，以 在坩堝110之底部與一側部之間不形成晶界。 第3 A-3C圓顯示用以在坩禍110中鑷造幾何型多晶石夕之 铺排例。晶粒工程V以藉由小心之晶種產生、定向、放置 20 與晶體成長來達成。例如，第3A與3B圖顯示其上顯示不同 (110)方向之兩單晶矽板片155、165。兩板片具有一垂直於 其表面之共同（100)方向，接著，切割各單晶矽板片155、 165，以形成許多成為晶種之矽塊15〇、160。表面種類可以 由於紋理的緣故而是均一的，或者依需要選擇。晶粒之形 30 201229330 狀與尺寸可以依據由單晶石夕板片155與165之鋪片的切割來 選擇，如第3B圖所示。在矽塊150、16〇之相鄰鋪片間的相 對方位角度決定在所得鑄態幾何型多晶矽中之晶界種類 (如，高角度、低角度或兩者）。例如，在第3八圖中顯示（1〇〇) 5極方向之兩晶粒方位。 第3C圖所示之晶種包含多數與其相鄰鋪片具有特定方 位關係之鋪排早晶石夕塊150、160，且該等石夕塊jo、160係 鋪排在坩堝110之底部，如第3C圖所示，使兩（11〇)方向交 錯如在石夕塊150、160上畫出之箭號所示。在此應注意石夕 1〇塊150、160晝成大致正方形塊僅是為了說明及下述之原 因，且可以是其他形狀。 雖然未顯示在第3C圖中，晶種亦可位在掛禍之側邊， 如第2圖所示。接著，可將矽進料（圖未示）導入坩堝ιι〇而位 在矽塊150、16〇上方並且使之熔化。或者，可將熔融矽倒 15入坩堝110中。在另一例中，先使坩堝110之溫度非常靠近 或上升至石夕之溶化溫度，並接著倒入該炼融>5夕。依據本發 明之實施例，該等晶種之薄層可以在固化開始前熔化。 接著，在前述任一例中，將該坩堝110冷卻，藉此，利 用例如一使熱輻射至大氣且熱仍可施加至坩堝11〇開口頂 20部之固體散熱材料，由該坩堝11〇底部（且如果晶種亦鋪排 在侧面則亦由側部）散熱。如此，當該晶種保持一固體狀態 時，加入熔化之矽，且該熔化物之方向性固化使柱狀晶粒 向上成長。依此方式，所得之幾何型多晶矽鑄塊將模擬鋪 排矽晶種150、160之晶粒方位。一旦適當地實施這方法後， 31 201229330 可將所得之鑄塊切成水平板片，以作為其他鎮造製程用之 晶種層。該板片可以具有一坩堝或其他用於鑄造之容器之 表面，如底面的尺寸與形狀或大致之尺寸與形狀。例如， 只有一這種板片可用於進行禱造製程。 5 第4圖顯示第3C圖中所示之鋪排的變化例，其中鑄態幾 何型多晶矽之晶粒方位之一例係將晶種塊15〇、160以一垂 直於坩堝110底部之共同極方向（〇〇丨)鋪排。在第4圖中，該 (110)方向族之所有變化呈現在矽塊15〇、16〇之鋪排中，如 方向箭號所示。雖然未在這特定圖中顯示，但是晶種亦可 10 以在坩堝110之一或多側上。 如此，在一用以形成矽之種晶方位可選定為使特定晶 界形成在鑄態幾何型多晶矽中，且其中前述晶界包圍幾何 形狀。相對於本發明之實施例，習知鑄造方法包括以一不 艾控制之方式藉由方向性固化而由一塊完全熔化之矽來鑄 15造該等多晶晶粒。所得之晶粒基本上具有任意之方位與尺 寸分布，且該任意晶粒方位難以有效使該矽表面形成紋 理。此外，在典型成長方法之天然產品、晶界中之扭折會 集結有關錯位之團或線之結構缺陷。這些錯位及它們會吸 引之雜質會造成電載子之迅速重組與作為光電材料之效能 2〇下降。因此，依據本發明之實施例，可達成小心計晝與種 入—規則晶界網路以鑄造單晶或幾何型多晶矽之目的，使 晶粒之尺寸、形狀與方位清楚地被選擇成可使少數載子壽 命達到最長且消除最多雜質，並且使結構缺陷減至最少者。 晶界可以選定為呈平坦之平面，以減少錯位成核並在 32 201229330 成長時維持其垂直方向 雜質與㈣應力之絲料消除 是表面方位)传選…:乂 “拉方位(特别 粒強;^ 成紋路、改善表面魏且增加晶 10 L X 。該等晶粒之尺寸係選定為可在有效減少距離與 收面積之間得職適當平衡者，例如，可實質幾何型 夕曰曰夕之鱗造’使該幾何型多晶⑪具有至少大約0.5cm至大 勺10cm之平均最小晶粒橫截面，且共同極方向垂直於該鱗 心成何型多晶石夕之表面，如第3C與4圖所示。該平均晶粒橫 *T為大約〇.5cm至大約7〇cm，或7〇cm以上。最後的於 果疋可增加所得之光電材料之整體效率。 依據本發明之實施例，多數單晶矽種晶之幾何型結構 可以放置在一坩塥之至少一表面上，例如一坩禍之底面 上，其中該幾何型結構包括緊密堆積之多邊形。或者，多 數單晶矽種晶之幾何型結構可放置成使該幾何型結構包括 15緊密堆積六邊形，或具有菱形或三角形格隙之多邊形，如 第5與6圖所示。在另一替代例中，未使用多數單晶種晶， 可使用由一在先前單晶矽鑄造中產生之鑄塊以切割或其他 方式獲得之矽區段或板作為用以鑄造本發明單晶矽之單一 種晶。這種單一種晶可以具有與坩堝或用於進行鑄造之其 ^ Λ 他容器之表面相同的尺寸與形狀，或大致相同之尺寸與形 狀。第5圖顯示一緊密堆積六邊形17〇陣列之例子，相對於 此，第6圖顯示具有菱形或三角形格隙180、190之多邊形陣 列的例子。以下將詳細說明這兩種陣列，且前述任一種結 構亦可應用於用以鑄造一固態單晶矽體或一固態多晶矽體 33 201229330 之實施例，其中該種晶係放置在一坩堝之底面與側面兩者 上。 依據本發明之實施例，藉由鑄造一幾何型多晶矽體所 製得之矽晶粒可以一管柱方式成長。此外，這些晶粒可具 5 有相同或接近於由其形成之晶種的形狀。當製造具有這種 特定晶界之矽時，最好該晶界接面僅具有在一角落處會合 之三個晶界。如第5圖所示，種晶之六邊形結構170對於晶 種之鋪排是必要的，其中該晶體方位使在水平面中之原子 具有三重或六重對稱性，例如石夕之（111)。如此，第5圖顯示 10 —用於排列在一如第1與2圖所示之適當坩堝底部中之六邊 形組合一部份的平面圖，且其中之箭號顯示在該等晶種中 之矽晶體（110)方向的位向。 或者，對具有四重對稱性之方位而言，該等晶種之不 同幾何型結構可用以來在多數晶粒之間保持穩定、對稱之 15 晶界，且仍符合三晶界角落規則。例如，如果Θ是在（110) 方向與一具有一（100)極之八邊形主要側邊間的方位誤差， 且α是一格隙菱形之頂角，如第6圖所示，則當α=90°-θ時， 所有晶粒將具有相對於該（110)方向為對稱之晶界。在這例 子中，所有晶粒具有垂直於第6圖所示孓紙面的（100)極方 20 向。如此，第6圖是一用以排列在一如第1與2圖所示之適當 坩堝底部中之八邊形晶種以及菱形晶種180、190之組合一 部份的平面圖，且其中箭號顯示在該等晶種中之矽晶體之 (110)方向的方位。 第7圖是顯示本發明製備矽之例的流程圖，且依據第7 34 201229330 圖’方法7GG開始時可先選擇用於單晶碎或幾何型多晶石夕成 長之單晶矽種晶，並將單晶矽種晶排列在一坩堝中（步驟 705)。或者，一藉由切割或其他方式而由一單晶矽或依幾 何形狀規則排列多晶矽之鑄塊所獲得的單一板片可作為一 5單一種曰曰使用。接著，可將石夕進料加入該掛禍中（步驟71〇)。 然後，由頂部加熱該坩堝並由底部冷卻該坩堝之底部(被動 地或主動地，見步驟715)。在熔化時，監測該矽之熔化階 段，以追蹤且控制該固-液界面之位置（步驟72〇)。繼續進行 該矽之熔化階段，直到該單晶矽種晶之一部份熔化為止（步 10驟725)。一旦該單晶矽種晶之所需部份熔化後，結束該熔 化階段並開始晶體成長階段(步驟7 3 〇)。在該坩堝内讓晶體 單向與垂直地繼續進行成長，直到矽結晶化完成為止（步驟 735)。如果排列晶種以進行幾何型多晶矽成長，則該結晶 化步驟735將產生一具有柱狀晶粒之幾何型多晶矽鑄塊（步 15驟740)。或者，如果排列晶種以進行單晶矽成長，則該結 晶化步驟735將產生一單晶矽鑄塊(步驟745”最好，取出在 步驟740或745任一者中產生之鑄塊，以進行後續處理（步驟 750)。 如第8A圖所示，矽進料2〇〇可以例如兩種方式中之其令 20 一種加入含有晶種220之坩堝210中。首先，適當地以呈方 便尺寸塊體形態之固體矽進料2〇〇完全裝滿坩堝210，再將 該裝滿之坩堝210放在一鑄造站（圖未示）中。 如第8B圖所示，在坩堝21〇中之溫度分布係設定成使可 加熱在掛堝210中之矽進料頂部而使其熔化，且可主動地或 35 201229330 被動地冷卻底部以在坩堝21〇底部保持固態之晶種22〇， 即，使它們不會在矽進料200熔化時浮起。一固息散熱材料 230與坩堝210之底部接觸，以散熱至水冷壁。例如，散熱 材料230可以是一塊固體石墨，且可較佳地具有等於或大於 5 s玄掛禍底部之尺寸。依據本發明，例如，當使用具有底面 為66cmx66cm之坩堝時，該散熱材料可為 66cmx66cmx20cm。較佳地，坩堝210之側壁無論如何均不 會被冷卻，只要使晶種220僅位在坩堝210底部上即可。如 果晶種220位在掛禍210底部與側壁兩者上，則散熱材料230 10將會放置在坩堝210底部與側壁兩者上以保持所需之熱分 布0 矽進料200之熔化狀態受到密切地監測，以追蹤在溶化 石夕與該等晶種間之界面位置。較佳地，炼化物24〇(顯示在 第8B圖中）繼續產生直到除了晶種22〇以外之所有石夕進料 15 200完全熔化為止，然後，晶種220將部份地熔化。例如， 藉由維持在該坩堝中另一處到達矽之熔化溫度後，在該掛 禍外表面上測量時之AT大約等於或小於01〇c/min ,可以密 切地控制加熱，使該等晶種220不會完全熔化。較佳地，藉 由維持在該坩堝中另一處到達矽之熔化溫度後，在該坩堝 20外表面上測量時之ΔΤ大約等於或小於〇.〇5°C/mm，可以密 切地控制加熱。例如，依據本發明，該^丁可在該坩堝之外 表面上於該坩堝與一大塊石墨之間測得，且一深度標尺可 插入熔化物240中以測量該熔化物之深度，並計算已熔化之 晶種220的部份。 36 201229330 如第8C圖所示，部份250顯示晶種220總厚度之熔化部 份。在晶種220之一部份250在熔化物240下方熔化後，該熔 化階段將迅速地結束且開始晶體成長階段，其中在坩堝21〇 頂部之加熱減少及/或在散熱材料230底部之冷卻增加。這 5過程之一例係顯示於第8D圖之圖表，且其中晶種220之一部 份250的熔化為時間的函數。如第8D圖所示，該等晶種具有 在5與6cm之間之初始厚度的一部份逐漸炫化，直到留下正 好2cm以下之固態晶種為止。例如，藉由維持在該坩堝中另 一處到達矽之熔化溫度後’在該坩堝外表面上測量（例如透 10過一安裝在該冷卻裝置中之熱電偶）時之ΔΤ大約等於或小 於0·l〇C/mm，可以密切地控制加熱，使該等晶種22〇不會完 全熔化。較佳地，藉由維持在該坩堝中另一處到達矽之熔 化溫度後，在該坩堝外表面上測量時之^丁大約等於或小於 〇.〇5°C/min，可以密切地控制加熱。此時，該熔化階段將迅 15速地結束且開始晶體成長階段，而這種情形係以在該圖表 之縱座標上測之固態厚度之大幅上升來表示。 接著’如第8E圖所示，在坩禍21〇内，晶種繼續單向地 且垂直地進行㈣成長，直到我晶化完成為止。當在該 坩堝210内之頂至底溫度梯度整平時，該鑄造循環結束。然 2〇後，整個鑄塊260將緩慢地冷卻至室溫。為了鑄造幾何型多 晶石夕’如第8E圖所示，這晶種單向成長產生柱狀晶粒27〇， 且該等晶粒27G具有與在它形成於其上之各個晶種22〇形狀 ^致相同的水平«面。依此方式，可簡先選擇該鎮態 多晶石夕之晶界。又’任何前叙晶種圖案/鋪排方式均可應 37 201229330 用於這鑄造方法中。 或者，為了鑄造單晶矽，晶種220可排列成完全沒有晶 界，以產生鑄態單晶矽。如第8F圖所示，部份250顯示晶種 220在該熔化物240下方之總厚度的熔化部份。在晶種220之 5 部份250於熔化物240下方熔化後，該熔化階段將迅速地結 束且開始晶體成長階段，其中在坩堝210頂部之加熱減少及 /或在散熱材料230底部之冷卻增加。接著，如第8G圖所示， 在坩堝210内，晶種繼續單向地且垂直地進行晶體成長，直 到矽結晶化完成為止。一以實質平坦較佳之固-液界面285 10 繼續向上且遠離該坩堝210之底面擴展，且當在該坩堝21〇 内之頂至底溫度梯度整平時，該鑄造循環結束。然後，整 個鑄塊280將緩慢地冷卻至室溫。為了鑄造幾何型多晶石夕， 如第8G圖所示，這晶種單向成長產生一連續鑄態單晶矽固 體 290。 15 在另一方法中’如第9圖所示’可以先在一分開室或分 開熔化容器300中熔化矽進料200。晶種220可以在熔融進料 305經由熔化管310送入或倒入坩堝210之前，由頂部部分地 或非部份地熔化’然後如參照第8 B - 8 G圖所述般地進行冷卻 與成長。在另一實施例中，矽種晶可以安裝在坩堝21〇之壁 20 (圖未示）上且可如前所述地由坩堝210之側邊與底部進行晶 體成長。或者，矽進料2〇〇可在一與坩堝210分開之熔化容 器300中熔化，且此時將坩堝21〇加熱至矽之熔化溫度，並 且控制§亥加熱，使晶種220不會完全炫化。在石夕進料2〇〇部 份熔化時，熔融進料3〇5可以由熔化容器300轉移至坩堝21〇 38 201229330 中，且可開始冷卻與結晶化。如此，依據本發明之實施例， 該固態結晶㈣之1份可包括晶種22G。或者，該等晶種 可在炫化物加入之前保持完全固態。此時，在溶化容器3〇〇 中之溶融妙被加熱到超過該溶化溫度，且當加入過熱液體 5時’该過熱液體可炼化某些晶種之一部份。 在一如第9圖所示之兩階段鑄造站中，熔融進料305將 由熔化谷器300向下倒入並落在晶種22〇上，且在固化時呈 現它們的結晶性。或者，溶化可在-中央炼化容器3〇〇令發 X中央溶化各器3〇〇對如一或多份掛禍2i〇(圖未示） 鑄造步驟更適當化；半連續却 依需要以一規律之方式發生， )之組分散固化_結構進行供料。依據本發明之實施 i "亥等可以在該等^^之側邊與底部内概晶種 220。这方法之某些優點包括：分開熔化與固化系統，使各 半連續地熔化矽，其中溶化新材料可 式發生，以維持坩堝供應；當由中間 之炼化物對該等固化站進行供料時，石夕會在頂部結潰(且可 進行底部之排出），使初始特料之純度增加；及使炼化容 器3〇〇可與㈣進_5達成平衡且不再成為鶴之雜質來The other pole directions of the Ul can be perpendicular to the bottom of the crucible. Moreover, in an embodiment, the (etc.) seed crystals may be arranged such that a common pole direction is perpendicular to the bottom of the crucible. When a single crystal stone is made by a conventional method such as the CZWZ method, and is produced by a cylindrical molten crystal (a), the obtained single crystal stone is smeared, for example, a vortex defect (by Such as vacancies and self-gap atoms special in the formation of defects) and (10) ring defects and. These vortex defects can be measured by X-ray images and are "vortexed, presented in the financial sector, and can be detected after the appearance of the preferential acid (4). 10 15 20 According to the conventional CZ or FZ method, The oxygen atoms in Shi Xi and the distribution in the Shi Xi are in the radial direction. This means that they will be arranged in a garment shape, a spiral shape or a stripe-shaped ring defect system with a central axis as a symmetry. Wherein the nano-scale oxygen precipitates are aggregated in a cylindrical band in the pull-out stone or in the crystal, to form a stack defect, and these cylindrical bands are visible in the disposable towel after the preferential acid is described. Both the vortex defect and the 0SF ring defect may be made by the casting process of the embodiment of the present invention due to the pull-out/method of the pool-melting impurity (four) (four) 单晶 single crystal 曰 右 = right opposite, and there is no (four) vortex defect produced by the casting process of the embodiment of the present invention. And (10) ring defects. This is due to the fact that in the rhyme, and in the whole curing and cooling process, the whole = warm line is generally flat, and the defects generated during the casting process are randomly distributed at the growth interface. And will not turn to influence. Regarding the light element impurity inversion in the eve of the different methods, the following series shown in Table 1 of 2012 201229330 are generally considered characteristic values. Table 1 Concentration (atoms/cmj) Oxygen carbon nitrogen floating zone <lxl〇16 <1χ1016 <lxl〇14 Czochralski 2xl017-lxl〇18 <1χ1016 casting 2-3xl〇17 2x10 丨6-5χ1017 >lxl〇 Part of the 15 CZ ingot can be made as low as 5xl〇17atoms/cm3 of oxygen, but it can't be lower. The carbon and nitrogen concentrations can be increased in the FZ and CZ ingots by deliberately doping the 5 impurities, but the doping does not exceed the solid solubility limit in these processes (as it is in the cast material), and the doped casting The size of the block is not larger than 20cm. Conversely, ingots are typically supersaturated with carbon and nitrogen due to the design of the off-coat and furnace hot zones. Therefore, nitrides and carbides are deposited throughout the liquid phase due to liquid phase nucleation and growth. Further, according to an embodiment of the present invention, the as-cast single crystal block produced has the aforementioned impurity order and has a size of 50 x 50 x 20 cm3 and 60 x 60 x 5 cm3. These dimensions are by way of example only and should not be considered as an upper limit of the casting process of the present invention. For example, in terms of the number of impurity stages, a dissolved carbon concentration of about 1-5 x 1017 atoms/cm3, a dissolved oxygen concentration of about 15 2-3 X 1017 at 〇ms/cm3, and i _5 较佳 are preferable in the crucible cast according to the present invention. ! The dissolved carbon concentration of 〇i5at〇ms/cm3. In accordance with an embodiment of the present invention, it may be formed to have at least two at least about 20 cm each, for example, at least about 2 〇 cm on one side and a third size at least about 10 cm, and having about 1-5 x 1017 atmS The dissolved carbon concentration of /cm3, the dissolved oxygen concentration of about 2-3xl〇17at〇ms/cm3 20, and the solid single crystal stone of the dissolved carbon concentration of 1_5xl〇5atoms/cm3 or the approximate single crystal stone body, and the most Good is the as-cast body. Preferably, 24 201229330 may form a dissolved carbon having at least two at least about 30 cm each, for example, a size of at least about 30 cm on one side and at least about i〇cm, and having a dissolved carbon of about 1-5 x 1017 atoms/cm3. A solid 5 single crystal body or an approximately single crystal body having a concentration, a dissolved oxygen concentration of about 2-3 x 1 017 atoms/cm 3 , and a dissolved carbon concentration of 1-5 x 10 15 atoms/cm 3 , and preferably an as-cast steroid. More preferably, it may be formed to have at least two third dimensions each of at least about 35 cm, for example, at least about 35 cm on one side and at least about i〇cm, and having a dissolved carbon concentration of about 1-5×10 17 atoms/cm 3 , about A solid 10-cell single crystal body or an approximately single crystal body of 2-3X1017 atoms/cm3 dissolved oxygen concentration, and a dissolution concentration of l-5xlOl5 atoms/cm3, and preferably an as-cast steroid. Still more preferably, it may be formed to have at least two at least about 40 cm each, for example, a size of at least about 40 cm on one side and a third size of at least about 20 cm, and having a dissolved carbon concentration of about 1-5 x 1 017 atoms/cm3, approximately A dissolved oxygen concentration of 2-3 x 10 atoms/cm3, and a solid single crystal steroid or an approximately single crystal ruthenium having a dissolved carbon concentration of 1 - 5 x 1 〇 15 atoms/cm 3 , and preferably an as-cast steroid. Still more preferably, it may be formed to have at least two third dimensions each of at least about 50 cm, such as 'at least about 50 cm on one side and at least about 2 〇cm, and having a dissolved carbon concentration of about 1-5 x 1 Onatoms/cm3. A solid single crystal body or an approximately single crystal body having a dissolved oxygen concentration of about 2-3 x 1 〇 17 atoms/cm 3 and a dissolved carbon concentration of i_5 x l 〇 i 5 at 〇 ms / cm 3 20 , and is preferably an as-cast steroid. Yet more preferably, it may be formed to have at least two at least about 60 cm each, for example, a size of at least about 60 cm on one side and a third size of at least about 20 cm, and having a dissolved carbon concentration of about 1-5 x 1 017 atoms/cm3, approximately A solid-state single crystal body or an approximately single crystal body having a dissolved oxygen concentration of 2-3 x 1 017 atoms/cm 3 and a dissolved carbon concentration of 25 201229330 l-5xl015 atoms/cm 3 , and preferably an as-cast steroid. Still more preferably, the crucible is formed to have at least two at least about 70 cm each, for example, a size of at least about 70 cm on one side and a third dimension of at least about 20 cm, and having a dissolved carbon concentration of about 5 l - 5 x 1 017 atoms / cm 3 , A solid single crystal body or an approximately single crystal body having a dissolved oxygen concentration of about 2-3 x 1 〇 17 atoms/cm 3 and a dissolved carbon concentration of 1 - 5 x 1 ato 15 atoms/cm 3 , and preferably an as-cast steroid. In accordance with an embodiment of the present invention, a third dimension having at least two radial dislocations and/or impurities and having at least two dimensions of at least about 2 〇cm and at least about 10 cm may be formed, a dissolved carbon concentration of l-5xlOl7atoms/cm3, a dissolved oxygen concentration of about 2-3 x 1 〇 17 atoms/cm 3 , and a continuous single crystal or a single crystal of a dissolved carbon concentration of l -5 x 1 〇 5 at 〇 / cm 3 > 5 Xi body. Preferably, a third dimension of at least about 15 〇cm and at least about 1 〇cm, each having no or substantially no radial distribution defects and/or impurities, and having a minimum of at least about 15 雨cm, and having a thickness of at least about 15 〇 cm, may be formed. The dissolved carbon concentration of l-5xlOl7atoms/cm3, the dissolved oxygen concentration of about 2-3xiq1 atoms/cm3, and the continuous single crystal or the single crystal stone of l-5xl〇15at〇ms/cm3 . More preferably, y forms a third dimension that has no or substantially no radial distribution defects and/or impurities and has a size of at least about 20 at least 35 cm and at least about i〇cm, I and has about l- The dissolved carbon concentration of 5xlOl7atoms/cm3, the dissolved oxygen concentration of about 2_3xl017at〇mS/Cm3, and the continuous single crystal or the single crystal of the dissolved carbon concentration of l-5xl〇i5atoms/cm3. Moreover, more preferably, there is no/radial distribution defect and/or impurity having at least two dimensions of at least 26 201229330 of approximately 40 cm and a third dimension of at least approximately 2 〇cm, And having a dissolved carbon concentration of about 1-5 x 1 017 atoms/cm 3 , a dissolved oxygen concentration of about 2-3 x 017 atoms/cm 3 , and a dissolved single crystal rock of udo 丨 5ator ns / cm 3 , or a single crystal slab. Still more preferably, 5 may form a third dimension having no or substantially no radial distribution defects and/or impurities and having at least two dimensions of at least about 50 cm each and at least about 20 cm, and having about l-5 x l017 atoms/ The dissolved carbon concentration of cm3, the dissolved oxygen concentration of about 2-3 x 10 7 atoms/cm 3 , and the continuous single crystal corpus callosum or the nearly single crystal corpus callosum of the dissolved carbon concentration of i-5 x 1 015 atoms/cm 3 . Still more preferably, a third dimension of at least two dimensions of at least about 60 cm and at least about 20 cm each having at least two radial dislocation defects and/or impurities and having a thickness of at least about -5 x 1017 atoms/ A dissolved carbon concentration of cm3, a dissolved oxygen concentration of about 2-3 x 1 017 atoms/cm3, and a continuous single crystal corpus callosum or an approximately single crystal quinone body having a dissolved carbon concentration of 1 -5 X 10 15 atoms/cm 3 . Still more preferably, a third dimension having at least two dimensions of at least about 7 〇cm and at least about 20 cm each having no or substantially no radial distribution defects and/or impurities may be formed, and having about 1-5 x 1017 atoms. a dissolved carbon concentration of /cm3, a dissolved oxygen concentration of about 2-3xl017at 〇ms/cin3, and a continuous 20 single crystal corpus callosum or an approximately single crystal corpus callosum having a dissolved carbon concentration of 1-5xl015 atoms/cm3. The upper limit of the horizontal dimension of the Shixi scale produced in accordance with an embodiment of the present invention and having the aforementioned impurity concentration is determined only by the casting and niobium manufacturing techniques, and is not determined by the method itself. Thus, a solid state continuous early or nearly early solid with the aforementioned impurity concentration can be preferably formed and 27 201229330 has at least two of the same size as the third size of the casting block in the casting container. The dimensions, and one-to-one-cube or-rectangular solids, ί; if the single-crystal cast state is sturdy and sturdy, these dimensions refer to the length, width and height of the limbs. 10 15 20 任任(四)^Inventive example, the seed crystals in the process of transformation can be ingots, Ge ^ size and pure 'and have a simple and mixed single crystal stone eve: according to, the number of sub-arrangements Jing Miao, such as square, rectangular, due to the money of the quadrilateral. They can be shaped to facilitate laying, edge-to-edge or ''laying, and mating with a predetermined pattern. ^In addition, according to embodiments of the invention, most of the seeds can = (4) include all - or more on. By arranging - (4) = interesting crystals (4) (4) into a plurality of "like blocks", these seeds can be used. These seeds can also be made by using the monthly method of continuous application. The single crystal or continuous geometry polycrystalline sample is cut to form 'the seed crystal used in the subsequent casting process can be made by the initial casting process. For the single crystal material, it is best to make as few crystal seeds as possible. Covering the New Finance Department to avoid defects. Thus, the size or shape of one or more sides of the section or the other m parts, etc., in which the invention is placed or placed in the same manner Or substantially the size and shape. The method and apparatus for performing the core cutting of the present invention will now be described. However, it should be understood that these are not the only ways to form a flaw in accordance with the principles of the present invention. ' &_0« At the bottom surface of the bottom portion of the bottom portion 28 201229330 and the wall portion, such that it is closely abutted in the same orientation and forms a large and continuously oriented sheet 120, or they are closely offset by a predetermined wrong direction. Pick up The resulting crucible produces a particular grain boundary with a deliberately selected grain size. That is, to cast a geometric polysilicon, the resulting crystalline 5 polymorphic polycrystalline germanium will have a grain size equal to or will be about the size of the seed crystals. Preferably, the majority of the seed crystals 100 are laid out and placed to substantially cover the entire bottom of the crucible 110. Further, preferably, the crucible 10 is made of, for example, cerium oxide, tantalum nitride or a liquid capsule. The coating is removed from the coating to remove the crystallized crucible from the crucible 110. Further, the seed crystals may comprise a single sheet or a plurality of sheets having a desired Ba body orientation and having a thickness of from about 3 mm to about 100 nm. The sheet. Although shown in Figure 1 is a particular number and size of seed crystal 100', it will be readily appreciated by those of ordinary skill in the art that the number and size of such seeds can be increased or decreased depending on the application. 15 Referring to Fig. 2, the seed crystal 100 may also be placed on one or more of the side walls 130, 140 of the crucible 110. The seed crystal 1〇〇 may be placed on all four walls of the crucible 11〇, but for convenience Description The seed crystal 100 is only displayed on the side walls 13A, 14B. Preferably, the seed crystal 1放置 placed on the wall of the wall of the crucible 110 is columnar for crystal growth. Preferably, the placement is performed. Each of the columnar seeds on either wall of the wall of the crucible 40 will have the same grain orientation as the seed crystal placed directly beneath it and on the bottom of the crucible 110. When the geometric polycrystalline crucible grows, in this manner Placing the columnar seed crystals will help the geometrical grain growth to be as large as the height of the crucible 110. Still referring to Fig. 2, the advantage of this seed crystal 100 structure is that it is used to cast 29 201229330 A method of making a line with higher crystallinity and higher growth speed. For example, it can be made up of __ by cup, ^, , simpler, self-propelled by many stacked in - and in the form of 埚丨 且 and the stone The seed crystal of the recess of the "cup" 5 10 15 . Alternatively, the molten (10) person 1 such as the bottom and the four-walled stone "cup" may be stacked by a plurality of seed crystals in the "__^ cup" and the concave wall of the four walls. In another example, - If the refining temperature of the bottom to Shixi is maintained, and the solid state cup is raised and brought to the heat balance 1, the above-mentioned = miscellaneous sand is cooled 110, thereby making the heat such as __ heat The shaft-to-atmosphere rail will smash the solid heat-dissipating material (not shown) at the top of the opening of the 110 and the heat can still be applied to the bottom and side. In this manner, the resulting & hang 110 can be single crystalline or geometric polycrystalline (depending on the seed crystal 100 used and its orientation 6) and the crystallization is performed at a faster rate than known polycrystalline casting processes. For the re-routing process, a portion of the sides and bottom of the crystallized crucible block is removed by known methods. Preferably, most of the seed crystals such as the seed crystal 100 are arranged such that the common pole direction between the seed crystals 1 垂直 is perpendicular to the bottom and side portions of the crucible 110 to the bottom and side of the crucible 110 No grain boundaries are formed between the parts. The 3rd A-3C circle shows an example of the fabrication of a geometric polycrystalline stone in the disaster 110. Grain engineering V is achieved by careful seeding, orientation, placement 20 and crystal growth. For example, Figures 3A and 3B show two single crystal gusset sheets 155, 165 on which different (110) directions are displayed. The two sheets have a common (100) direction perpendicular to their surface, and then each of the single crystal gusset sheets 155, 165 is cut to form a plurality of seed crystal blocks 15 and 160. The surface type can be uniform due to the texture or can be selected as needed. Shape of the grain 30 201229330 The shape and size can be selected according to the cutting of the sheets of the single crystal plate 155 and 165, as shown in Fig. 3B. The relative azimuthal angles between adjacent tiles of the blocks 150, 16〇 determine the type of grain boundary (e.g., high angle, low angle, or both) in the resulting as-cast geometry polysilicon. For example, in Figure 3, (1〇〇) two grain orientations in the 5-pole direction are shown. The seed crystal shown in FIG. 3C includes a plurality of paving early crystal paving blocks 150, 160 having a specific orientation relationship with the adjacent paving sheets, and the joss blocks of the stone mats are arranged at the bottom of the crucible 110, such as the 3C. As shown in the figure, the two (11 〇) directions are staggered as indicated by the arrows drawn on the stone blocks 150, 160. It should be noted here that the stone blocks 1 and 150 are generally square blocks for the purpose of illustration and the following, and may be other shapes. Although not shown in Figure 3C, the seed crystals may also be on the side of the crash, as shown in Figure 2. Next, a crucible feed (not shown) can be introduced into the 坩埚ιι and positioned above the crucibles 150, 16 and melted. Alternatively, the melt can be poured into the crucible 110. In another example, the temperature of the crucible 110 is first brought close to or rises to the melting temperature of the stone, and then poured into the refining > In accordance with embodiments of the present invention, the thin layers of the seed crystals can be melted prior to the onset of curing. Next, in any of the foregoing examples, the crucible 110 is cooled, whereby the solid heat dissipating material that can be applied to the top portion 20 of the crucible 11 by heat, for example, is applied to the bottom of the crucible 11 And if the seed crystal is also laid on the side, it is also cooled by the side. Thus, when the seed crystal is maintained in a solid state, the molten crucible is added, and the directional solidification of the melt causes the columnar crystal grains to grow upward. In this manner, the resulting geometric polycrystalline germanium ingot will simulate the grain orientation of the seed crystals 150, 160. Once this method is properly implemented, 31 201229330 can be used to cut the resulting ingot into horizontal sheets for use as a seed layer for other finishing processes. The sheet may have a weir or other surface for the container being cast, such as the size and shape of the bottom surface or substantially the size and shape. For example, only one such sheet can be used to perform a prayer process. 5 Fig. 4 shows a variation of the arrangement shown in Fig. 3C, in which one of the crystal orientations of the as-cast polycrystalline germanium is such that the seed crystal blocks 15, 160 are in a common pole direction perpendicular to the bottom of the crucible 110 ( 〇〇丨) Paving. In Fig. 4, all changes in the (110) direction family are presented in the layout of the blocks 15〇, 16〇, as indicated by the direction arrows. Although not shown in this particular figure, the seed crystal may also be on one or more sides of the crucible 110. Thus, the orientation of the seed crystal used to form the germanium can be selected such that a particular grain boundary is formed in the as-cast geometry polysilicon, and wherein the grain boundaries enclose the geometry. In contrast to embodiments of the present invention, conventional casting methods include casting the polycrystalline grains from a fully melted crucible by directional solidification in an uncontrolled manner. The resulting grains have essentially any orientation and size distribution, and the arbitrary grain orientation is difficult to effectively shape the surface of the crucible. In addition, the kinks in the natural products and grain boundaries of typical growth methods will build up structural defects in the group or line of misalignment. These misalignments and the impurities they attract can cause rapid recombination of the electron carriers and a decrease in the effectiveness as a photovoltaic material. Therefore, according to the embodiment of the present invention, the purpose of careful counting and seeding-regular grain boundary network for casting single crystal or geometric polycrystalline silicon can be achieved, so that the size, shape and orientation of the crystal grains can be clearly selected so that The minority carrier life is the longest and eliminates the most impurities, and minimizes structural defects. The grain boundary can be selected to be a flat plane to reduce misalignment nucleation and maintain its vertical direction impurity when growing at 32 201229330 and (4) stress is removed by surface orientation.): 乂" Pulling orientation (special grain strength; ^ Graining, improve surface Wei and increase crystal 10 LX. The size of these grains is selected to be the appropriate balance between effective distance reduction and area. For example, the scale of the geometrical geometry can be Forming the geometric polycrystal 11 to have an average minimum grain cross section of at least about 0.5 cm to about 10 cm, and the common pole direction is perpendicular to the surface of the spheroid, such as 3C and 4 The average grain width *T is from about 〇5 cm to about 7 〇cm, or more than 7 〇cm. The final enthalpy can increase the overall efficiency of the resulting photovoltaic material. According to an embodiment of the invention, The geometry of most single crystal germanium seed crystals can be placed on at least one surface of a crucible, such as a bottom surface of a disaster, wherein the geometric structure includes closely packed polygons. Or, most single crystal germanium seed crystals Geometric structure can be placed The geometry is comprised of 15 closely packed hexagons, or polygons having diamond or triangular lattices, as shown in Figures 5 and 6. In another alternative, most single crystal seed crystals are not used and can be used A crucible section or plate obtained by cutting or otherwise obtained from an ingot produced in the previous single crystal crucible casting is used as a single crystal for casting the single crystal crucible of the present invention. This single crystal may have a crucible or For the casting, the surface of the container is the same size and shape, or substantially the same size and shape. Figure 5 shows an example of a closely packed hexagonal 17-inch array. In contrast, Figure 6 shows Examples of polygonal arrays of diamond or triangular lattices 180, 190. The two arrays will be described in detail below, and any of the foregoing structures can also be applied to the casting of a solid single crystal body or a solid polycrystalline body 33 201229330 For example, the crystal system is placed on both the bottom surface and the side surface of the crucible. According to an embodiment of the present invention, the crucible crystal grains obtained by casting a geometric polycrystalline crucible may be a column. In addition, the grains may have the same or close to the shape of the seed crystal formed therefrom. When manufacturing the crucible having such a specific grain boundary, it is preferable that the grain boundary junction has only a corner meeting. The three grain boundaries. As shown in Fig. 5, the seed hexagonal structure 170 is necessary for the seeding of the seed crystal, wherein the crystal orientation gives the atom in the horizontal plane a triple or six-fold symmetry, such as stone.夕之(111). Thus, Figure 5 shows a plan view of a portion of a hexagonal combination for arranging in a suitable bottom portion as shown in Figures 1 and 2, wherein the arrows are shown in The orientation of the 矽 crystal (110) direction in the seed crystals. Or, for the orientation with quadruple symmetry, the different geometric structures of the crystals can be used to maintain stability and symmetry between most grains. The 15 grain boundaries, and still meet the three-grain boundary rule. For example, if Θ is the azimuth error between the (110) direction and a major side of an octagon with a (100) pole, and α is the apex angle of a gap diamond, as shown in Figure 6, then When α = 90° - θ, all grains will have grain boundaries that are symmetrical with respect to the (110) direction. In this example, all of the dies have a (100) pole 20 direction perpendicular to the crepe plane shown in Fig. 6. Thus, Figure 6 is a plan view of a portion of a combination of octagonal seed crystals and diamond seed crystals 180, 190 arranged in a suitable crucible bottom as shown in Figures 1 and 2, and wherein the arrows The orientation of the (110) direction of the germanium crystals in the seed crystals is shown. Figure 7 is a flow chart showing an example of the preparation of ruthenium according to the present invention, and the single crystal bismuth seed crystal for single crystal or geometric polycrystalline growth can be selected first according to the method of Figure 734 201229330. The single crystal germanium seed crystals are arranged in a crucible (step 705). Alternatively, a single sheet obtained by cutting or otherwise arranging a single crystal crucible or a polycrystalline tantalum ingot in a regular shape may be used as a single sheet. Then, the Shixi feed can be added to the disaster (step 71). The crucible is then heated from the top and the bottom of the crucible is cooled from the bottom (passively or actively, see step 715). Upon melting, the melting stage of the crucible is monitored to track and control the position of the solid-liquid interface (step 72). The melting phase of the crucible is continued until one of the single crystal germanium seed crystals is partially melted (step 10, step 725). Once the desired portion of the single crystal germanium seed crystal is melted, the melting phase is terminated and the crystal growth phase is started (step 7 3 〇). The crystal is allowed to continue to grow unidirectionally and vertically in the crucible until the crystallization of the crucible is completed (step 735). If the seed crystals are arranged for geometric polysilicon growth, the crystallization step 735 will produce a geometric polycrystalline germanium ingot having columnar grains (step 740). Alternatively, if the seed crystals are arranged for single crystal germanium growth, the crystallization step 735 will produce a single crystal germanium ingot (step 745). Preferably, the ingot produced in either of steps 740 or 745 is removed. Subsequent processing is performed (step 750). As shown in Fig. 8A, the ruthenium feed 2 〇〇 can be, for example, in two ways, such that 20 one is added to the crucible 210 containing the seed crystal 220. First, suitably in a convenient size The solid crucible feed 2 in the form of a block is completely filled with crucible 210, and the filled crucible 210 is placed in a casting station (not shown). As shown in Fig. 8B, in Fig. 21 The temperature profile is set such that the top of the crucible feed in the hung 210 can be heated to melt, and the bottom can be passively cooled or actively held at 35 201229330 to maintain a solid seed crystal 22〇 at the bottom of the crucible 21〇, ie, They are not allowed to float when the crucible feed 200 melts. A retention heat dissipating material 230 is in contact with the bottom of the crucible 210 to dissipate heat to the water wall. For example, the heat dissipating material 230 may be a piece of solid graphite, and may preferably have Equal to or greater than the size of the bottom of the 5 s. According to the present invention, for example, when a crucible having a bottom surface of 66 cm x 66 cm is used, the heat dissipating material may be 66 cm x 66 cm x 20 cm. Preferably, the side wall of the crucible 210 is not cooled anyway, as long as the seed crystal 220 is positioned only at the bottom of the crucible 210. If the seed crystal 220 is on both the bottom and the side wall of the hazard 210, the heat dissipating material 230 10 will be placed on both the bottom and the side walls of the crucible 210 to maintain the desired heat distribution. The state of melting is closely monitored to track the interfacial position between the dissolved fossils and the seeds. Preferably, the refinery 24 〇 (shown in Figure 8B) continues to be produced until all but the seed 22 〇 After the stone feed 15 200 is completely melted, the seed crystal 220 will be partially melted. For example, by maintaining the melting temperature of the crucible at another point in the crucible, it is measured on the outer surface of the crucible. AT is approximately equal to or less than 01 〇 c/min, and heating can be closely controlled so that the seed crystals 220 do not completely melt. Preferably, by maintaining the melting temperature of the crucible at another point in the crucible, The 坩埚20 appearance The ΔΤ at the time of measurement is approximately equal to or less than 〇.〇5°C/mm, and the heating can be closely controlled. For example, according to the present invention, the bismuth can be on the outer surface of the crucible on the surface of the crucible and a large piece of graphite. Between measurements, and a depth gauge can be inserted into the melt 240 to measure the depth of the melt and calculate the portion of the molten seed crystal 220. 36 201229330 As shown in Figure 8C, portion 250 shows seed crystal 220. The molten portion of the total thickness. After one portion 250 of the seed crystal 220 is melted below the melt 240, the melting phase will quickly end and the crystal growth phase begins, wherein the heating at the top of the crucible 21〇 is reduced and/or The cooling of the bottom of the heat dissipating material 230 is increased. An example of these five processes is shown in the chart of Figure 8D, and wherein the melting of a portion 250 of the seed crystal 220 is a function of time. As shown in Fig. 8D, the seed crystals have a portion of the initial thickness between 5 and 6 cm gradually smeared until a solid crystal seed of exactly 2 cm or less is left. For example, by maintaining the melting temperature of the crucible at another point in the crucible, 'measured on the outer surface of the crucible (eg, through a thermocouple installed in the cooling device) is approximately equal to or less than zero. • l〇C/mm, the heating can be closely controlled so that the seed crystals 22〇 are not completely melted. Preferably, by maintaining the melting temperature of the crucible at another point in the crucible, the measurement on the outer surface of the crucible is approximately equal to or less than 〇.〇5 ° C / min, and the heating can be closely controlled. . At this point, the melting phase will end at a rapid rate and begin the crystal growth phase, which is indicated by a substantial increase in the solid thickness measured on the ordinate of the chart. Then, as shown in Fig. 8E, in the case of the disaster, the seed crystal continues to grow unidirectionally and vertically (4) until I complete the crystallization. The casting cycle ends when the top to bottom temperature gradient in the crucible 210 is leveled. After 2 turns, the entire ingot 260 will slowly cool to room temperature. In order to cast the geometric polycrystalline stone as shown in Fig. 8E, the seed crystal grows unidirectionally to produce columnar grains 27, and the crystal grains 27G have the respective seed crystals 22 on which it is formed. The shape ^ is the same level «face. In this way, the eutectic polycrystalline stone granules can be selected briefly. Also, any pre-synthesis pattern/layout method can be used in this casting method in accordance with 37 201229330. Alternatively, in order to cast single crystal germanium, the seed crystals 220 may be arranged to be completely free of grain boundaries to produce as-cast single crystal germanium. As shown in Fig. 8F, portion 250 shows the melted portion of the total thickness of seed crystal 220 below the melt 240. After the portion 250 of the seed crystal 220 is melted below the melt 240, the melting phase will quickly end and the crystal growth phase begins, with reduced heating at the top of the crucible 210 and/or increased cooling at the bottom of the heat dissipating material 230. Next, as shown in Fig. 8G, in the crucible 210, the seed crystal continues to crystal growth unidirectionally and vertically until the crystallization of the crucible is completed. A solid-liquid interface 285 10 that is substantially flat and preferably continues to expand upwardly and away from the bottom surface of the crucible 210, and the casting cycle ends when the top-to-bottom temperature gradient in the crucible 21〇 is leveled. The entire ingot 280 will then slowly cool to room temperature. In order to cast the geometric polycrystalline stone, as shown in Fig. 8G, the seed crystal grows unidirectionally to produce a continuous as-cast single crystal solid body 290. 15 In another method, as shown in Fig. 9, the crucible feed 200 may be first melted in a separate chamber or separate melting vessel 300. The seed crystal 220 may be partially or non-partially melted from the top before the molten feed 305 is fed or poured into the crucible 210 via the melt tube 310 and then cooled as described with reference to Figure 8B-8G. growing up. In another embodiment, the seed crystal can be mounted on the wall 20 (not shown) of the crucible 21 and can be crystal grown from the sides and bottom of the crucible 210 as previously described. Alternatively, the crucible feed 2 can be melted in a melting vessel 300 separate from the crucible 210, and at this time, the crucible 21 crucible is heated to the melting temperature of the crucible, and the heating is controlled so that the seed crystal 220 is not completely dazzled. Chemical. The molten feed 3〇5 can be transferred from the melting vessel 300 to 坩埚21〇 38 201229330 and the cooling and crystallization can begin, as the 夕 进 feed 2 熔化 part melts. Thus, in accordance with an embodiment of the present invention, one part of the solid crystalline (tetra) may include seed crystal 22G. Alternatively, the seeds can remain completely solid before the addition of the scent. At this time, the melting in the melting vessel 3 is heated to exceed the melting temperature, and when the superheated liquid 5 is added, the superheated liquid can refine a part of some of the crystals. In a two-stage casting station as shown in Figure 9, the molten feed 305 will be poured down from the molten granulator 300 and onto the seed crystal 22, and will exhibit their crystallinity upon solidification. Alternatively, the melting process can be more appropriate in the - central refining vessel 3, the central melting of each of the three reactors, such as one or more parts of the accident 2i〇 (not shown), the casting step is more appropriate; semi-continuous but as needed The regular way occurs, the group is dispersed and solidified _ structure is fed. According to the implementation of the present invention, i "Hai et al. may crystallize 220 in the side and bottom of the ^^. Some of the advantages of this method include: separate melting and solidification systems, such that each semi-continuous melting of the crucible, wherein the melting of the new material can occur to maintain the supply of rhodium; when the refining station is fed from the intermediate refining station , Shi Xi will collapse at the top (and can be discharged at the bottom), so that the purity of the initial special material is increased; and the refining vessel 3 can be balanced with (4) into the _5 and no longer become the impurity of the crane.
您坩埙底部尺寸與形狀相同， 而该鑄塊之其餘部份可切成 39 201229330 磚與晶圓以加工成光電電池。或者，整個禱塊可、 平板片，以在多數鑄造站中作為種晶使用，以、M切成水 後之鑄造工作。 亍多數以 在本發明實施例之方法中使用的矽進料可含有 個如選自於包括：硼、鋁、鋰、鎵、碟、 雜劑。這些摻雜劑之總量可以大約是0< 或多 銻、砷及鉍之摻 .01份每百萬原子％ (ppma)至大約2PPma。較佳地，在該矽中之摻雜劑量係— 使由該矽製成之晶圓具有大約〇.1至大約50ohm_ 可 約0.5至大約5.0ohm-cm較佳之電阻的量 cm，且以大 10 如此，依據本發明，該矽可以是最好鑄態連續單晶矽 體或鑄態連續幾何型多晶矽體’且大致沒有或沒有如=sf 及/或旋渦缺陷等徑向分布缺陷。該妙體之至少兩尺寸宜至 少大約為10cm，且至少大約20cm為佳，並且至少3〇cm更 佳，而又以至少40cm更佳，並以至少5〇cm更佳，且以至少 15 60cm尤佳，更以至少大約70cm最佳。最佳地，這矽體之第 三尺寸至少大約5cm，且以至少大約i5cm為佳，並且以至 少大約20cm最佳。較佳地，該矽體可具有至少兩各與一鑄 造谷器内部尺寸一樣大之尺寸。如在此所說明者，本發明 可用以利用一簡單且低成本之鑄造方法製造大單晶矽體或 20 幾何型多晶矽體。 以下是本發明實施例之實驗例，且這些例子只是用以 舉例與說明本發明之實施例，並且無論如何均不應被視為 會限制本發明之範疇。Your bottom is the same size and shape, and the rest of the ingot can be cut into 39 201229330 bricks and wafers for processing into photovoltaic cells. Alternatively, the entire prayer block can be used as a seed crystal in most casting stations to make the M work after cutting into water. Most of the ruthenium feed used in the process of the embodiments of the present invention may contain, for example, be selected from the group consisting of boron, aluminum, lithium, gallium, dish, and dopant. The total amount of these dopants may be about 0 <RTI ID=0.0>0>>> Preferably, the doping amount in the crucible is such that the wafer made of the crucible has a mass of about 0.1 to about 50 ohms, preferably about 0.5 to about 5.0 ohm-cm, and is large. Thus, in accordance with the present invention, the crucible may be a preferably as-cast continuous single crystal crucible or an as-cast continuous geometric polycrystalline crucible' with substantially no or no radial distribution defects such as =sf and/or vortex defects. Preferably, at least two dimensions of the body are at least about 10 cm, and at least about 20 cm is preferred, and at least 3 cm is preferred, and more preferably at least 40 cm, and more preferably at least 5 cm, and at least 15 60 cm. Especially good, it is best at least about 70cm. Most preferably, the third dimension of the body is at least about 5 cm, and preferably at least about i5 cm, and most preferably at least about 20 cm. Preferably, the body may have at least two dimensions each as large as the inner dimensions of a caster. As explained herein, the present invention can be used to fabricate large single crystal germanium or 20 geometric polycrystalline germanium using a simple and low cost casting process. The following is an experimental example of the present invention, and these examples are only intended to illustrate and illustrate the embodiments of the present invention, and should not be construed as limiting the scope of the present invention.
Ml 40 201229330 晶種製備：使用一塗覆有帶鋸之鑽石，沿其長向切割 一由MEMC公司所取得且具有〇 3ppma之硼的純柴式（cz) 石夕（單晶）晶坯，使它具有每側14cm測量值之正方形橫截 面。接著’使用相同之鋸通過其橫截面切割所得之單晶矽 5塊成多數具有厚度大約為2cm至大約3cm之板>1，且這些板 片係作為單晶矽種晶或“晶種，，。保持該矽晶坯之（100)結晶 極方位，且將所得之單一晶體矽板片配置在一石英坩堝底 部’使該板片之（1〇〇)方向面向上，並且該（11〇)方向保持與 該掛禍之一側平行。該石英坩堝具有一側為68cm之正方形 10 橫載面、大約4〇cm之深度、及大約i.8cm之壁厚度。該等板 片配置在該琳堝底部且它們的長尺寸平行於該坩堝底部， 而它們的側邊互相接觸以在該坩堝底部上形成一單一且完 整之板片層。 鑄造：接著，於室溫下在該坩堝中裝入總質量為265kg 15之固體矽進料，再將已裝填之坩堝置入一用以鑄造多晶矽 之現場熔化/方向固化鑄造站。該熔化製程係利用將電阻加 熱器加熱至大約1550°C來進行，且該等加熱器係構成為可 由頂部加熱且熱可藉由開啟絕緣體總共6 c m而輻射出該底 。這結構可使熔化在一由頂部向下之方向上朝該坩瑪底 20部進行，且透過底部之被動冷卻使該等種晶可在熔化溫度 下保持固態，並可藉由一熱電偶加以監測。溶化之程产係 利用一每10分鐘便下降至該熔化物中的石英深度標尺2測 量，且比較該深度標尺高度與一在該站中之空坩堝所取得 之測量值，以決定剩餘固體材料之高度。藉由深度標尺= 201229330 量，該進料先炼化，接著熔化狀態持續至僅留下大約l 5cm 高度之種晶。此時，藉由將絕緣體開啟至12cm，加熱功率 下降至- 1500。(：之溫度設定值，且由底部之輕射增加。在 固化開始之前，深度標尺測量觀察到種晶會再多熔化一或 5兩毫米。接著，晶種之單-晶體繼續成長直到固化步驟結 束為止。該成長階段與剩餘之鑄造循環係以其中頂至底部 溫度梯度整平之-般參數來進行，且接著讓整個鑄塊緩慢 地冷卻至室溫。該鑄態矽產物是一 66cmx66cmx2〇cm之鑄 塊，且其具有50cmx50cm之橫截面的中央部份由頂至底部 1〇是單晶石夕。該單晶石夕結構可由目視檢查該鑄塊表面而看 出，此外，以一可描繪出晶界之鹼性配方蝕刻該矽可進一 步證實在該材料中沒有晶界。該整體摻雜平均值是 1.2ohm-cm，且由這矽製成之光電電池具有16 〇%之電效率。 在依據這例子所進行之其他鑄造操作中，可觀察到該 15铸態矽產物係含有其他晶體位向之較小矽晶體之連續一致 矽晶體，或者是一具有多數相鄰多晶矽區域之單晶矽體。 例2 晶種製備：晶種係如例1中一般地完成，但是該單晶矽 晶種被切割成使一半晶種之（110)方向係位在相對該等正方 20形晶種側邊呈45度處，而另一半晶種具有大約20度之角 度《該等正方形塊係以兩不同晶種方位交錯之棋盤方式層 狀地排列在該坩堝底部，即，相對該等坩堝側邊之方位， 該（110)方向具有45度角與20度角，而該等晶種互相相對地 具有25度或155度之錯向。但是，由於該等正方形晶種尺寸 42 201229330 並不一致，所以在該晶種層中的某些間隙並未受到覆蓋。 該坩堝在各正方形側上之測量值大約為33cm，且高度測量 值大約為22cm。 鑄造：將有該等晶種之坩堝與另一總共含有560進料 5矽塊之坩堝放入一普遍存在铸造法（UCP)兩階段鑄造站 中，接著將收納坩堝(該等晶種在其内）加熱至矽之熔點，但 並未給予可完全熔化之能量。在另一坩堝中之矽則利用電 阻石墨加熱器以至少超過矽熔化溫度5〇c>c以上之溫度加以 熔化，且接著倒入該收納坩堝中。此時，隨即開始固化， 10且熱由該收納坩堝底部抽出，以進行單向固化與種晶成 長。由於该等晶種構成之已固化材料的質量，標準之成長 循環會縮紐。依此方式，並非在冷卻製程開始前提供讓所 有66kg(l〇kg之晶種與56kg之進料矽）固化之時間，而是僅為 56kg熔融矽提供時間，以避免浪費加熱能量。這方法之產 物疋具有大且大致柱狀晶粒之石夕塊，且具有形狀與尺寸 接近它們形成於其上之初始種晶之頂面尺寸的正方形橫截 面。當成長進行時，橫向晶界位置有時會偏移。 例3 晶種製備：種晶係以用以内襯一坩堝底部之23竑乘 2〇方、（1〇〇)之板完成，且該等板提供一63cmx63cm之覆蓋面 積及一由中心3cm至側邊1.8cm的厚度，且所有的板係配置 成其（110)方向與該掛堝之壁呈45。。 鑄造：以另一總共24 2k g之進料矽塊填充含有該等晶種 之坩堝，產生一本質矽、由先前鑄塊回收之矽、及具有一p 43 201229330 架電阻大於9ohm-cm之雙鑄態料混合物。接著將在制 渦中之妙進料送人—階段方向固化爐中，且將觸禍(該等 矽於其内）加熱至1550°C’並藉由開啟絕緣體至12cm來冷卻 10 15 底I5 411)·液界φ在；^化時仍保持大致平坦，因此在溶化 I。束0夺’沒有任何部份之晶齡完錄穿。财之厚度係 利用-石英深度標尺監測，且當測得—中心厚度為2⑽ 時^熔化階段停止，且加熱溫度下降至i44〇〇C並且絕緣 體高度增加至15em。由魅相改變開始，在騎财另一 處到達碎之^:化溫錢於贿禍外表面上測得之溫度增加 之速度便保持在或低於Ο」％/—。才妾著，繼續進行剩餘之 (· 固化製程’且對加熱器保持大致固定之功率直到觀察到結 晶成長結束為止。在成長結束後，使該結晶料塊之溫度 梯度達到整平狀態並接著均勻地下降至室溫。在由該明 中取出該鑄塊後，將該鑄塊底部切下一大塊以便在另一後 續鑄Ufi序中再利用作為—晶種，且該_塊之剩餘部份則 切成多數12.5em乘方之碑以進-步加工。該製程成功地使 單結晶實質在整财層橫截面上成長，且—直進行至該禱 塊頂部。又，藉由檢視該切割矽可看出單結晶性。 在依據這例子進行之其他鑄造工作中，可發現該鑄態 2 〇矽產物係含有其他晶體位向之較小矽晶體之連續一致矽晶 體，或者是一具有多數相鄰多晶矽區域之單晶矽體。 由本發明實施例之矽製成的晶圓具有適當薄度且可使 用在光電電池中，此外，該等晶圓可以是n型或p型者。例 如，晶圓可以具有大約1〇微米之厚度至大約7〇〇微米之厚 44 201229330 度。另外，在光電電池中使用之晶圓最好具有大於該晶圓 厚度⑴之擴散長度(Lp)。例如，Lp對t之適當比例至少為0.5。 例如，它可以至少為大約1.1或至少為大約2。該擴散長度 是少數載體(如在P型材料中之電子)在與大多數載體(在p型 5材料中之電洞）再組合之前可擴散之平均距離，且該Lp與少 數載體壽命τ有關而其關係為Lp=(Dt)1/2，其中D是擴散常 數。該擴散長度可以利用多種方法測量，例如光子束感應 電流（Photon-Beam-Induced Current)法或表面光電壓 (Surface Photovoltage)法等。例如，如何可測量擴散長度的 10 說明請參見A. Fahrenbruch與R. Bube之Achademic Press， 1983, ρρ· 90-102, “Fundamentals of Solar Cells”。 該等晶圓可具有大約100毫米至大約600毫米之寬度， 且較佳地’该等晶圓具有至少一至少為大約50mm之尺寸。 由本發明之矽製成之晶圓及因此由本發明製成之光電電池 15可具有，例如，大約50至3600平方公分之表面積。該晶圓 之前面最好具有紋路，例如，該晶圓可利用化學蝕刻、電 聚钮刻、或雷射或機械刻劃形成紋路。如果使用一具有（100) 極方位之晶圓’可利用在一如氫氧化鈉之鹼性水溶液中， 於如大約7G°C至大約9G°C之高溫下處理該晶圓 ，以餘刻該 20 曰曰圓形成一具各向異性紋路之表面。該水溶液可含有如異 丙醇等醇類。 1 | | 匕’太陽能電池可以使用由本發明實施例之鑄態矽 塊產生之晶81來製備，其方法包含：切割該鑄態梦固體以 形成至少—曰間 θ曰圓；在該晶圓表面上選擇性地進行一清潔程 45 201229330 序；在該表面上選擇性地進行一形成紋理步驟；藉由，例 如，摻雜該表面而形成一p-n接面；在該表面上選擇性地沈 積一抗反射塗層；藉由，例如，一銘燒結步驟而選擇性地 形成選自一背面場與一鈍化層之至少一層；及在該晶圓上 5 形成導電接頭。一鈍化層是一與一裸晶圓表面具有界面之 層，且該界面束缚住表面原子之懸鍵。在石夕上之純化層的 例子包括氮化矽、二氧化矽與非晶質矽。該層通常薄於1微 米，可以是透光的或者作為一反射層。 在一利用如一 p型矽晶圓之用以製備一光電電池的典 10 型與一般方法中，該晶圓之一側露於一適當η摻雜劑，以在 該晶圓之前面或光接收側形成一射極層與p-n接面。通常， 藉由利用如化學或物理沈積等一般使用之方法先將η摻雜 劑沈積在該Ρ型晶圓前面，且在此沈積後，將如構等摻雜劑 驅入該矽晶圓之前面以使該η摻雜劑再擴散進入該晶圓表 15 面，可形成該η型層或射極層。這“驅入”步驟通常是利用使 該晶圓暴露於高溫下來達成，因此，一p-n接面會形成在該 η型層與該p型矽晶圓基材間的邊界區域處。在磷或其他摻 雜劑形成該射極層之前，該晶圓表面可形成紋路。為了再 改善光吸收性，可選擇性地在該晶圓前面塗布一如氮化石夕 20 等抗反射塗層，有時提供同時形成表面及/或整體鈍化。 為了使用因使該p-n接面暴露於光能而產生之電位，該 光電電池通常在該晶圓前面設有一導電前電接頭且在該晶 圓背面設有一導電後電接頭，但是兩接頭可均位在該晶圓 背面。這些接頭通常是由一或多個高導電性金屬製成，且 46 201229330 因此通常是透明的。 如此，依據前述實施例製成之太陽能電池可包含··一 由實質上沒有徑向分布缺陷之連續單晶矽體形成之晶圓， 且該石夕體可為如前所述者並且具有例如，至少兩各至少大 5 約為25cm之尺寸及一至少大約為20cm之第三尺寸；一在該 晶圓中之p-n接面；一在該晶圓表面上的選擇性抗反射塗 層；最好具有選自於一背面場與一鈍化層之至少一層；及 在該晶圓上之導電接頭，其中該石夕體可以實質上沒有旋渦 缺陷且實質上沒有OSF缺陷。 同時，依據前述實施例製成之太陽能電池亦可包含： 一由一連續幾何型多晶矽體形成之晶圓，且該石夕體具有一 預定晶粒方位結構，並且一共同極方向垂直於該矽體之表 面，且該矽體最好具有至少兩各至少大約為1〇cm2尺寸； -在該晶圓中之Ρ·η接面；-在該晶圓表面上的選擇性抗反 W射塗層；最好具有選自於-背面場與—鈍化層之至少一 層；及在該晶圓上之導電接頭，其中該幾何型多晶石夕包括 具有大約0.5cm至大約30cm之平均晶粒橫截面之石夕晶粒且 其中該矽體可以實質上沒有旋渦缺陷 陷。 且實質上沒有OSF缺 20 發明所屬技術領域中具有通常知識者可知在不偏離本 發明㈣與精神之情形下可對所揭露之結構與方法進行各 種修改與變化，例如，㈣㈣彡成單“之所揭露製程與 方法亦可應用於形成近似單晶矽、 、 已在此說明了，夕之鑄造，但是在不，、組合。此外’雖然 I在不偏離本發明料與精神 47 201229330 形下鑄造其他半導體材料與非金屬結晶材料。例如， 明人已可依據本發明實施例铸造其他材料，例如石申化 豕、緒切、氧化紹、氣化鎵、氧化鋅、硫化鋅、珅化鎵 綈化銦、錯、紀鋇氧化物、鑭氧化物、鎮氧化物、及 /、他半導體、氧化物、及具有液相之金屬互熔化合物。藉 由考慮在此揭露之本發明說明書與實施，發明所屬技術領 域中具有通常知識者可了解本發明之其他實施例 。本說明 書與例子應僅被為舉例，而本發明之真正範脅與精神係由 以下申請專利範圍顯示。 10 【圖式簡單說明】 第1圖顯示本發明實施例之在一坩堝底面上的一矽晶 種結構例； 第2圖顯示本發明實施例之在一坩堝底面上的另一矽 晶種結構例； 15 第3A-3C圖顯示本發明實施例之用以在一坩堝十鑄造 依幾何形狀規則排列多晶矽之鋪排(tiling)例； 第4圖顯示本發明實施例之用以在一坩堝中鑄造依幾 何形狀規則排列多晶矽之另一鋪排例； 第5圖顯示本發明實施例之緊密堆疊鹵晶種鋪片陣列； 20 第6圖顯示本發明實施例之具有斜方形或三角形格隙 之多邊形形狀的陣列例； 第7圖顯示本發明實施例之方法例；及 第8A-8G與9圖顯示本發明實施例之單晶矽或依幾何 形狀規則排列多晶矽之鑄造製程例。 48 201229330 【主要元件符號說明 100.. .晶種 110.. .坩堝 120.. .板片 130.140.. .側壁 150,160…石夕塊 155,165…單晶矽板片 170.. .六邊形 180，190…菱形或三角形格隙 200".矽進料 210".坩堝 220.. .晶種 230.. .散熱材料 240…熔化物 250.. .晶種之一部份 260…鑄塊 270.. .晶粒 280…鑄塊 285.. .固-液界面 290.. .連續鑄態單晶矽固體 300.. .溶化容器 305…熔融進料 310…熔化管 700.. .方法 705,710,715,720,725,730,735,740, 745,750.··步驟 49Ml 40 201229330 Seed preparation: a pure chai (cz) stone (single crystal) crystal blank obtained by MEMC and having a boron of 3 ppma was cut along its long direction using a diamond coated with a band saw. It has a square cross section with a measured value of 14 cm per side. Then, using the same saw, the resulting single crystal crucible 5 is cut into a plurality of sheets having a thickness of about 2 cm to about 3 cm, and these sheets are used as single crystal germanium seed crystals or "seeds," Maintaining the (100) crystal polar orientation of the twins, and arranging the resulting single crystal crucible sheet at the bottom of a quartz crucible to make the (1 〇〇) direction of the slab face up, and The direction remains parallel to one side of the hang. The quartz crucible has a square 10 cross-plane of 68 cm on one side, a depth of about 4 〇cm, and a wall thickness of about i.8 cm. The bottoms of the enamels are parallel to the bottom of the crucible and their sides are in contact with each other to form a single and complete sheet layer on the bottom of the crucible. Casting: Next, in the crucible at room temperature A solid ruthenium feed having a total mass of 265 kg 15 is placed, and the filled ruthenium is placed in an on-site melting/direction solidification casting station for casting polycrystalline silicon. The melting process is performed by heating the electric resistance heater to about 1550 ° C. Carry out, and the heaters are It can be heated by the top and the heat can be radiated out by opening the insulator a total of 6 cm. This structure can be melted in a top-down direction toward the bottom of the gamma 20, and passive cooling through the bottom The seed crystals can remain solid at the melting temperature and can be monitored by a thermocouple. The melting process is measured using a quartz depth scale 2 that drops to the melt every 10 minutes and compares the depth. The height of the scale and the measured value obtained in the space in the station to determine the height of the remaining solid material. With the depth gauge = 201229330, the feed is refining, and then the molten state continues until only about l At 5 cm height, the heating power drops to -1500 by opening the insulator to 12 cm. (: The temperature setting is increased by the bottom light. Before the curing starts, the depth scale measurement observes the species. The crystals are further melted by one or five millimeters. Then, the single crystal of the seed crystal continues to grow until the end of the curing step. The growth phase and the remaining casting cycle are top to bottom. The gradient is leveled to the general parameters, and then the entire ingot is slowly cooled to room temperature. The as-cast tantalum product is a 66 cm x 66 cm x 2 cm ingot and has a central portion of 50 cm x 50 cm cross section. The top to bottom 1〇 is a single crystal stone. The single crystal structure can be visually inspected for the surface of the ingot, and further, etching the crucible in an alkaline formulation capable of delineating the grain boundary can further confirm the material. There is no grain boundary. The overall doping average is 1.2 ohm-cm, and the photovoltaic cell made of this has an electrical efficiency of 16%. In other casting operations according to this example, it can be observed. The 15 as-cast tantalum product is a continuous uniform crystal containing other crystals with smaller crystals, or a single crystal body having a plurality of adjacent polycrystalline germanium regions. Example 2 Seed preparation: The seed system was generally completed as in Example 1, but the single crystal seed crystal was cut such that the (110) direction of the half seed was tied to the side of the square 20 seed crystal. 45 degrees, and the other half of the seed has an angle of about 20 degrees. The square blocks are layered at the bottom of the crucible in a checkerboard pattern with two different crystal orientations, ie, the orientation relative to the sides of the crucible. The (110) direction has an angle of 45 degrees and an angle of 20 degrees, and the seeds have opposite directions of 25 degrees or 155 degrees with respect to each other. However, since the square seed sizes 42 201229330 are not consistent, some of the gaps in the seed layer are not covered. The enthalpy has a measured value of approximately 33 cm on each square side and a height measurement of approximately 22 cm. Casting: placing the crucible with the seed crystals and another crucible containing a total of 560 feeds in a two-stage casting station in a ubiquitous casting (UCP) process, followed by storage of the crucibles (these seeds are in it) Heated to the melting point of the crucible, but did not give energy that could be completely melted. In the other case, the graphite graphite heater is used to melt at a temperature at least 5 〇 c > c above the enthalpy melting temperature, and then poured into the enthalpy. At this point, curing begins, 10 and heat is drawn from the bottom of the containment crucible for unidirectional solidification and seed crystal growth. Due to the quality of the cured materials made up of these seeds, the standard growth cycle will shrink. In this way, it is not necessary to provide a time for all 66 kg (100 kg of seed crystals and 56 kg of feed crucible) to be solidified before the start of the cooling process, but only 56 kg of molten crucible is provided to avoid wasting heating energy. The product of this method has a large and substantially columnar grain of a stone block and has a square cross-section with a shape and size close to the top surface size of the initial seed crystal on which they are formed. When the growth progresses, the lateral grain boundary position sometimes shifts. Example 3 Seed preparation: The seed crystal system was completed with a plate of 23 竑 by 2 〇 square, (1 〇〇) lining the bottom of a raft, and the plates provided a coverage area of 63 cm x 63 cm and a center from the center of 3 cm to the side The sides are 1.8 cm thick and all the plates are arranged such that their (110) direction is 45 with the wall of the hanging. . Casting: filling the crucible containing the seed crystals with another total of 24 2 kg of feedstock to produce an intrinsic crucible, recovered from the previous ingot, and having a p 43 201229330 frame resistance greater than 9 ohm-cm Cast material mixture. Then, the wonderful feed in the vortex is sent to the stage-stage curing oven, and the accident is heated to 1550 ° C' and cooled by opening the insulator to 12 cm. 10 15 bottom I5 411 The liquid boundary φ remains substantially flat during the formation, so it melts in I. The bundle 0 won't have any part of the crystal age to finish recording. The thickness of the wealth is monitored using a quartz depth gauge, and when measured - the center thickness is 2 (10), the melting phase is stopped, and the heating temperature drops to i44 〇〇 C and the insulator height increases to 15 em. Starting from the change of the charm, the other part of the ride is broken. The temperature increase on the surface of the money is kept at or below Ο%%. Then, continue to carry out the remaining (·curing process) and maintain a substantially constant power to the heater until the end of crystal growth is observed. After the growth is completed, the temperature gradient of the crystal block is leveled and then uniform Underground down to room temperature. After the ingot is taken out of the mold, the bottom of the ingot is cut into large pieces for reuse in another subsequent casting Ufi sequence, and the remaining part of the block The portion is cut into a majority of 12.5em squares for further processing. The process successfully allows the single crystal to grow substantially in the cross section of the whole grain layer, and proceeds straight to the top of the prayer block. Again, by examining the The single crystallinity can be seen by cutting the crucible. In other casting work according to this example, it can be found that the as-cast 2 〇矽 product contains continuous crystals of other crystals with smaller crystals, or one has Single crystal germanium in most adjacent polysilicon regions. Wafers made from tantalum of the present invention have suitable thinness and can be used in photovoltaic cells, and in addition, the wafers can be either n-type or p-type. Wafer can Having a thickness of about 1 〇 micron to a thickness of about 7 〇〇 microns 44 201229330 degrees. In addition, the wafer used in the photovoltaic cell preferably has a diffusion length (Lp) greater than the thickness (1) of the wafer. For example, Lp versus t A suitable ratio is at least 0.5. For example, it may be at least about 1.1 or at least about 2. The diffusion length is a minority of carriers (such as electrons in a P-type material) and most carriers (in a p-type 5 material) The average distance over which the hole can be diffused before recombination, and the Lp is related to a minority carrier lifetime τ and the relationship is Lp = (Dt) 1/2, where D is the diffusion constant. The diffusion length can be measured by various methods, for example Photon-Beam-Induced Current or Surface Photovoltage. For example, how to measure the diffusion length. 10 See A. Fahrenbruch and R. Bube, Achademic Press, 1983, ρρ· 90-102, "Fundamentals of Solar Cells." The wafers may have a width of from about 100 mm to about 600 mm, and preferably the wafers have at least one dimension of at least about 50 mm. The wafer fabricated by the invention and thus the photovoltaic cell 15 made by the present invention may have, for example, a surface area of about 50 to 3600 square centimeters. The front surface of the wafer preferably has a grain, for example, the wafer may utilize chemistry Etching, electro-convex engraving, or laser or mechanical scribing to form a grain. If a wafer with a (100) polar orientation is used, it can be used in an alkaline aqueous solution such as sodium hydroxide, for example, at about 7G ° C The wafer is processed to a temperature of about 9 G ° C to form an anisotropic grain surface with the remaining 20 turns. The aqueous solution may contain an alcohol such as isopropyl alcohol. 1 | | 太阳能 'Solar cell can be prepared using the crystal 81 produced by the as-cast block of the embodiment of the present invention, the method comprising: cutting the as-cast dream solid to form at least - inter-turn θ 曰 circle; on the surface of the wafer Selectively performing a cleaning process 45 201229330; selectively performing a texturing step on the surface; forming a pn junction by, for example, doping the surface; selectively depositing a surface on the surface An anti-reflective coating; selectively forming at least one layer selected from a back surface field and a passivation layer by, for example, a sintering step; and forming a conductive joint on the wafer 5. A passivation layer is a layer having an interface with a bare wafer surface, and the interface binds the dangling bonds of the surface atoms. Examples of the purified layer on Shi Xi include tantalum nitride, cerium oxide and amorphous germanium. This layer is typically thinner than 1 micron and may be light transmissive or as a reflective layer. In a typical method and a general method for fabricating a photovoltaic cell using a p-type germanium wafer, one of the wafers is exposed to an appropriate η dopant for front side or light reception of the wafer. The side forms an emitter layer and a pn junction. Generally, an η dopant is first deposited in front of the ruthenium wafer by a method generally used, such as chemical or physical deposition, and after deposition, a dopant such as a structure is driven into the ruthenium wafer. The n-type layer or the emitter layer may be formed by re-diffusion of the η dopant into the surface of the wafer surface 15 . This "drive-in" step is typically achieved by exposing the wafer to elevated temperatures, so that a p-n junction is formed at the boundary region between the n-type layer and the p-type germanium wafer substrate. The surface of the wafer may form a grain before the phosphor or other dopant forms the emitter layer. In order to further improve the light absorption, an anti-reflective coating such as Nitride Quaternary 20 may be selectively applied in front of the wafer, sometimes providing simultaneous surface formation and/or integral passivation. In order to use the potential generated by exposing the pn junction to light energy, the photovoltaic cell is generally provided with a conductive front electrical connector on the front side of the wafer and a conductive rear electrical connector on the back surface of the wafer, but both connectors may be Located on the back of the wafer. These joints are typically made of one or more highly conductive metals, and 46 201229330 is therefore generally transparent. As such, the solar cell fabricated in accordance with the foregoing embodiments may comprise a wafer formed of a continuous single crystal body having substantially no radial distribution defects, and the stone body may be as described above and have, for example At least two each having a size of at least about 5 cm and a third dimension of at least about 20 cm; a pn junction in the wafer; a selective anti-reflective coating on the surface of the wafer; Preferably, there is at least one layer selected from a back surface field and a passivation layer; and an electrically conductive joint on the wafer, wherein the stone body can be substantially free of vortex defects and substantially free of OSF defects. Meanwhile, the solar cell fabricated according to the foregoing embodiment may further include: a wafer formed of a continuous geometric polycrystalline body, and the stone body has a predetermined grain orientation structure, and a common pole direction is perpendicular to the crucible The surface of the body, and the body preferably has at least two dimensions of at least about 1 〇 cm 2 ; - a Ρ η junction in the wafer; - a selective anti-reflective coating on the surface of the wafer a layer; preferably having at least one layer selected from the group consisting of a back surface field and a passivation layer; and an electrically conductive joint on the wafer, wherein the geometric polycrystalline stone includes an average grain cross-section having a thickness of from about 0.5 cm to about 30 cm The stone of the cross section and wherein the body can be substantially free of vortex defects. And there is substantially no OSF deficiency. It is obvious to those skilled in the art that the present invention can be modified and changed without departing from the spirit and scope of the invention. For example, (4) (4) The disclosed processes and methods can also be applied to form approximately single crystal germanium, which has been described herein, but not in, and in combination. Further, although I does not deviate from the present invention, the material and spirit 47 201229330 Other semiconductor materials and non-metallic crystalline materials. For example, Mingren has been able to cast other materials according to embodiments of the present invention, such as Shishenhua, Xuan, Oxidation, Gallium Sulfide, Zinc Oxide, Zinc Sulfide, Gallium Antimonide Indium, erbium, cerium oxide, cerium oxide, oxidized oxide, and/or other semiconductors, oxides, and metal intermetallic compounds having a liquid phase. By considering the present specification and implementation disclosed herein, Other embodiments of the invention may be understood by those of ordinary skill in the art. The present specification and examples should be considered as merely exemplary, and the true scope and essence of the present invention. The god system is shown by the following patent application. 10 [Simplified description of the drawings] Fig. 1 shows an example of a seed crystal structure on a bottom surface of an embodiment of the present invention; Fig. 2 shows an example of the embodiment of the present invention. Another example of a seed crystal structure on the bottom surface; 15 3A-3C shows an example of a tiling for regularly arranging polycrystalline germanium in a ten-tenth casting according to an embodiment of the present invention; and FIG. 4 shows an embodiment of the present invention. For example, another layout example in which a polycrystalline crucible is regularly arranged according to a geometric shape is cast in one crucible; FIG. 5 shows a closely stacked halogen seeding patch array according to an embodiment of the present invention; 20 FIG. 6 shows an embodiment of the present invention having An example of an array of polygonal shapes of a rhombic or triangular lattice; FIG. 7 shows an example of a method of an embodiment of the present invention; and FIGS. 8A-8G and 9 show a single crystal crucible according to an embodiment of the present invention or a polycrystalline crucible arranged according to a geometrical shape. Example of casting process. 48 201229330 [Main component symbol description 100.. . Seed crystal 110.. .坩埚120.. .Slab 130.140.. .Side wall 150,160...石夕块155,165...Single crystal plate 170.. .6 Edge 180 190...diamond or triangle gap 200".矽feed 210".坩埚220... seed crystal 230.. heat dissipation material 240...melt 250.. one of the seed crystals 260...ingot 270.. Grain 280... ingot 285.. solid-liquid interface 290.. continuous cast single crystal ruthenium solid 300.. melt vessel 305... melt feed 310... melt tube 700.. method 705,710,715,720,725,730,735,740, 745,750. ··Step 49